AffA
United Sr»t3j
Env:,x>nrr»ntal Protection
Agency
Of.'ice of Solid Waste
and Pmergency Resoonse
Washington. DC 20460
£PA,530-SW-87
OcTofier 1987 .
Solid Want
Characterization of MWC Ashes
and Leachates from MSW Landfills,
Monofills, and Co-Disposal Sites
Volume V of VII
Characterization of Municipal Waste
Combustor Residues
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FINAL DRAFT
CHARACTERIZATION OF MUNICIPAL WASTE
COMBUSTOR RESIDUES
VOLUME V OF VII
Versar, Inc
6850 Versar Center
P.O. Box 1549
Springfield, Virginia 22151
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Contract No. 68-03-3235
Delivery Order Mo. 3
FINAL DRAFT REPORT
CHARACTERIZATION OF MUNICIPAL
WASTE COMBUSTOR RESIDUES
Prepared for:
Robert P. Hartley
U.S. Environmental Protection Agency
Hazardous Waste Engineering Research Laboratory
26 West St. Clair Street
Cincinnati, Ohio 45263
Prepared by:
Versar Inc.
6850 Versar Center
P.O. Box 1549
Springfield, Virginia 22151
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TABLE OF CONTENTS
1.0 INTRODUCTION 1-1
1.1 Background 1-2
1.2 Objective 1-4
1.3 Summary of Approach 1-5
2.0 REVIEW OP PERTINENT LITERATURE 2-1
3.0 APPROACH TO STUDY 3-1
3.1 Municipal Waste Combustor Facility Selection 3-1
3.1.1 Facility Selection Criteria 3-1
3.1.2 Identification and Selection Process 3-3
3.1.3 Conformance to Selection Criteria 3-4
3.2 Facilities Selected 3-2
3.2.1 Facility A 3-7
3.2.2 Facility B 3-10
3.2.3 Facility C 3-12
3.2.4 Facility D 3-15
3.2.5 Summary of Facility Design and Operating
Characteristics 3-17
3.3 Samples and Sampling Procedures 3-13
3.3.1 Facility A 3-21
3.3.2 Facility B 3-27
3.3.3 Facility C 3-34
3.3.4 Facility D 3-45
3.4 Sample Preparation and Analysis Procedures 3-52
3.4.1 Laboratory Leachates 3-53
3.4.2 Analyses 3-58
4.0 RESULTS AND DISCUSSION 4-1
4.1 Facility Operating Parameters 4-1
4.2 Solid Samples 4-6
4.2.1 Metals 4-6
4.2.2 Polychlorinated Biphenyls (PCBs) 4-11
4.2.3 Polychlorinated Dibenzo-p-dioxins and
Polychlorinated Dibenzo-furans (PCDD/PCDFs) 4-17
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TABLE OF CONTENTS
(Continued)
4.3 Laboratory Leachates 4-29
4.3.1 Metals 4-29
4.3.2 Polychlorinated Dibenzo-p-dioxins and
Pol/chlorinated Dibenzo-furans 4-34
4.4 Field Water Samples 4-40
4.4.1 Metals 4-40
4.4.2 Polychlorinatad Biphenyls 4-44
4.4.3 Polychlorinatad Dibenzo-p-dioxins and
Polychlorinated Dibenzo-Furans (PCDD/PCDFs) 4-45
4.4.4 Organic Constituents 4-51
4.5 Quality Assurance/Quality Control Summary 4-56
4.5.1 Internal QA/QC 4-57
4.5.2 External OA/QC 4-80
5.0 EVALUATION 5-1
5.1 Comparative Evaluation With Previously Reported
Information 5-1
5.1.1 Solid Samples 5-2
5.1.2 Laboratory Leachates 5-5
5.1.3 Field Water Samples 5-10
5.2 Significant Trends in the Data from this Study 5-14
5.2.1 Metals 5-14
5.2.2 Polychlorinated Biphenyls, Polychlorinated
Dibenzo-p-dioxins, and Polychlorinated
Dibenzo-f urans 5-19
5.3 Relationships Between Facility Design and Operating
Characteristics and Contaminant Concentrations 5-22
5.3.1 Metals 5-23
5.3.2 Polychlorinated Biphenyls, Polychlorinated
Dibenzo-p-dioxins, and Polychlorinated
Dibenzo-f urans 5-23
5.4 Overall Assessment of Risk 5-23
5.4.1 Metals 5-23
5.4.2 Polychlorinated Biphenyls 5-25
5.4.3 Polychlorinated Dibenzo-p-dioxins 5-25
6.0 CONCLUSIONS 6-1
APPENDIX A - References
APPENDIX B - Analytical Methods for PCDD/PCDFs
APPENDIX C - Analytical Methods for PCBs
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LIST OP TABLES
Table 1.1 Samples Collected From MWC Facilities 1-7
Table 1.2 Numbers of Analyses Performed 1-9
Table 3.1 Facility Conformance to Selection Criteria 3-5
Table 3.2 Municipal Waste Combustor Design and Operating
Characteristics 3-19
Table 3.3 Landfill Characteristics 3-20
Table 3.4 Sample Identification Codes for Facility A 3-23
Table 3.5 Sample Identification Codes for Facility B 3-29
Table 3.6 Sample Identification Codes for Facility C 3-37
Table 3.7 Sample Identification Codes for Facility D 3-46
Table 3.8 Summary Conditions for £P, TCLP, and MWEP Methods 3-54
Table 3.9 Summary of Analytical Methods and Detection Limits 3-59
Table 4.1 Summary of Facility A Operating Parameters 4-2
Table 4.2 Summary of Facility B Operating Parameters 4-3
Table 4.3 Summary of Facility C Operating Parameters 4-4
Table 4.4 Summary of Facility 0 Operating Parameters 4-5
Table 4.5 Total Metals Data for Solid Samples 4-3
Table 4.6 PCBs in Solid Samples 4-12
Table 4.7 PCDD and PCDF in Solid Samples 4-13
Table 4.8 Extractable Metals Data for Three Laboratory
Leaching Procedures 4-31
Table 4.9 PCDD and PCDF in Laboratory Leachate Samples (TCLP) 4-35
Table 4.10 Extractable Organics Data for Three Leaching
Procedures 4-36
Table 4.11 Total Metals Data for Field Water Samples 4-41
Table 4.12 PCBs in Field Water Samples 4-46
Table 4.13 PCDD and PCDF in Field Water Samples 4-48
Table 4.14 Organic Constituents in Field Water Samples 4-52
Table 4.15 QC Summary (Internal) for Metals 4-58
Table 4.16 QC Summary (Internal) for PCS Analysis 4-63
Table 4.17 QC Summary (Internal) for PCDD/PCDF Analysis 4-69
Table 4.18 QC Summary (Internal) for Organic Analysis 4-76
Table 4.19 QC Summary (External) for Metals 4-81
Table 4.20 QC Summary (External) for PCS Analysis 4-85
Table 4.21 QC Summary (External) for PCDD/PCDF Analysis 4-88
Table 4.22 QC Summary (External) for Organic Analysis 4-92
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LIST OF TABLES
(Continued)
Table 5.1 Comparative Evaluation of Total Metals in Solid
Samples 5-3
Table 5.2 Comparative Evaluation of PCBs in Solid Samples 5-4
Table 5.3 Comparative Evaluation of PCDD/PCDFs in Solid
Samples 5-6
Table 5.4 Comparative Evaluation of Metals in EP Leachates 5-8
Table 5.5 Comparative Evaluation of Metals in TCLP Leachates 5-9
Table 5.6 Comparative Evaluation of Metals in Deionized
Water Leachates 5-11
Table 5.7 Comparative Evaluation of Total Metals in Field
Water Samples 5-12
Table 5.3 Comparative Evaluation of BNAs in Field Water
Water Samples 5-13
Table 5.9 Summary Results for Metals 5-15
Table 5.10 Summary Results for PCBs, Dioxins, and Furans 5-20
LIST OF FIGURES
Figure 3.1 Facility A Combustor 3-8
Figure 3.2 Facility B Combustor 3-11
Figure 3.3 Facility C Combustor 3-13
Figure 3.4 Facility D Combustor 3-16
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ACKNOWLEDGEMENTS
This report was prepared by the staffs of Technical Operations and
Laboratory Operations at Versar, Inc. and by Battelle, Columbus
laboratory, Versar's subcontractor for analyses of municipal waste
combustor residues for polychlorinated dibenzo-dioxins and
polychlorinated dibenzo-furans. The contributions of the following
individuals are gratefully acknowledged.
Versar Inc.
• Dr. Wesley L. Bradford, Project Manager, Senior Hydrogeologist
• Mr. Arthur Jung, Task Manager, Senior Environmental Scientist
• Mr. David Basko, Environmental Engineer
• Ms. Pamela Hillis, Chemical Engineer
Battelle, Columbus
• Dr. Fred DeRoos, Senior Analyst
The assistance and guidance of Mr. Robert P. Hartley during all
phases of this project is gratefully acknowledged.
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1.0 INTRODUCTION
This report is the final deliverable for Delivery Order Number 3 of
Contract 68-03-3235. The report (I) describes the planning, sampling and
analysis activities; (2) summarizes the results of chemical analyses
performed on fly ash, bottom ash, laboratory-prepared leachates of fly
ash and bottom ash, field-collected quench water, leachate from
mono-filled residue landfills, and ground water from monitoring wells
located near the landfills; and (3) evaluates the results of analyses
with respect to municipal waste combustor (MWC) facility design and
operation, variations among leachate preparation procedures, and
characterization of the residues as hazardous wastes.
The remainder of this section discusses the background of this
contract, the objectives of the study conducted under Delivery Order
No. 3, and briefly summarizes the technical approach taken in this study.
Section 2 presents the results of a limited review of published
literature characterizing MWC residues.
Section 3 describes the approaches Versar took in selecting MWC
facilities for sampling and analyses, describes the design and
operational characteristics of the MWC facilities selected and their
associated mono-filled landfills, describes the sampling procedures and
samples collected at each MWC facility, and the sample handling and
analysis procedures.
Section 4, presents and discusses the results of analyses of samples
collected at the facilities by sample matrix (fly ash, bottom ash,
laboratory-prepared leachate, quench water, landfill leachate, ground
water) and by major constituent category (heavy metals, polychlorinated
biphenyls (PCB's), polychlorinated dibenzo-dioxins and polychlorinated
dibenzo-furans (PCDD/PCDP), and other organic constituents).
Subsection 4.5 discusses the results of internal and external
quality assurance/quality control (QA/QC) procedures exercised on the
analyses of the samples.
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In Section 5 the data obtained in this project is analyzed and
evaluated in several respects. In Subsection 5.1 the data is compared
with selected data from the published literature and from other generally
unpublished sources. In Subsection 5.2 comparisons are made between the
concentrations of constituents measured in laboratory-prepared leachates
(Extraction Procedure, Toxicity Characteristic Leaching Procedure, and
the Mono-filled Waste Extraction Procedure) and concentration of
constituents measured in field-collected water samples (quench water,
field leachate and ground water). The objective of this comparative
evaluation is to determine whether any of the extraction procedures
currently required, or contemplated as being required in the future, for
regulatory testing simulate actual environmental extraction processes.
Subsection 5.3 provides a qualitative evaluation of the relationships
observed in this study between MWC facility design and operating
characteristics and the concentration of constituents observed in the
residues. Subsection 5.4 provides an overall assessment of the hazardous
waste characteristics of MWC residues.
The conclusions of this study are summarized in Section 6.
1.1 Background
This project was conducted under Delivery Order No. 3 of Contract
68-03-3235 administered through the U.S. EPA Hazardous Waste Engineering
Research Laboratory, Cincinnati, Ohio. This contract was originally
entitled "Evaluation of Site Characteristics Contributing to Pollution at
Selected Hazardous Waste Disposal Sites".
Delivery Order No. 1 of this contract dealt with the selection of a
limited number of hazardous waste disposal sites from several hundred
existing sites nationwide for in-depth study of site and contaminant
characteristics contributing to contaminant migration off-site. Delivery
Order Mo. 1 was completed in July, 1985 with submittal of a final report
detailing the approach used in evaluating and selecting candidate sites
for in-depth investigation, and recommending five candidate sites, from
which one would be selected.
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Delivery Order No. 2 involved five Tasks: (I) establishing working
relationships with the selected site owner/operator; (2) preparing a
detailed work plan for investigations at the site; (3) acquiring existing
site information; (4) conducting the investigation as planned, and (5)
reporting the results of the investigation. Delivery Order No. 2 was
completed through Task 3. Tasks 4 and 5 were cancelled due to changing
priorities within the Agency and to potential conflicts that the proposed
investigation might cause with ongoing litigation at the candidate sites
selected.
Delivery Order No. 2 was amended in February, 1986 creating a new
Task 4 calling for an evaluation of the effectiveness of line/fly ash
injection for stabilizing a typical solid waste landfill. Task 4 could
not be completed because of unforeseen problems gaining access to
landfills both privately and publicly owned for purposes of investigation.
The results of the attempts to gain access to landfills were reported by
letter in March and April, 1986.
Delivery Order No. 3 of this contract, issued in July, 1986, called
for chemical characterization of residues from municipal waste combustor
facilities. The title of the contract was changed to "Characterization
of Municipal Waste Combustor Residues". The performance and findings of
the study conducted under this delivery order are reported herein.
At the present time, the solid residues from MWC facilities are
typically classified as non-hazardous and are placed in landfills
regulated under Subtitle D of the Resource Conservation and Recovery Act
(RCRA).
Studies on the solid residues conducted in the past few years,
however, have shown the presence of heavy metals and organic compounds in
concentrations of potential concern. Extraction Procedure (EP) Toxicity
Tests performed on fly ash samples have shown that the concentrations of
some metals (primarily cadmium , chromium and lead) in the EP leachate
regularly exceed the maximum concentrations for the hazardous waste
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characteristic of EP Toxicity. In addition, polychlorinated dibenzo-
dioxins (PCDDs), polychlorinated dibenzo-furans (PCDFs), and polychlorinated
biphenyls (PCBs) have been found in the fly ash and flue gas from MWCs.
PCDDs and PCDFs have been reported in fly ash samples from MWCs in the
United States, Canada, Europe, and Japan.
The presence of some heavy metals in the EP leachate from fly ash at
concentrations exceeding the regulatory limits, and the presence of
potentially highly toxic organic compounds (PCDDs and PCDFs) in fly ash
have raised questions concerning the proper disposal of MWC residues in
general. Of special concern is the issue of whether MWC residues
disposal is adequately regulated under Subtitle D of RCRA. In order to
determine (1) whether an alternative regulatory strategy is needed for
MWC residues and (2) the structure of an alternative regulatory strategy,
scientifically-defensible data chemically characterizing MWC residues are
needed.
The database presently available on chemical characterization,
however, is limited in size and scope (chemicals tested for). Moreover,
the available data have generally been obtained using inconsistent
sampling techniques and analytical methodologies, and using uncertain or
inadequate quality assurance/quality control procedures.
Work is underway under other EPA contracts to assemble information
on MWC residues from other sources (stata agencies, MWC facility '
operators, etc.), and initiatives have been submitted for chemical
characterization studies during Fiscal Years 1987 and 1988. It is
expected that neither of these efforts will provide the scientifically-
defensible data needed for evaluation/development of alternative
regulatory strategies by the end of Fiscal Year 1937 when the Agency is
required to provide a preliminary report to Congress on this issue.
1.2 Objective
The objective of this project performed under this Delivery Order is
to collect chemical characterization data on residues from municipal waste
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combustor (MWC) facilities. The residues characterized include fly ash
from air emission control equipment, bottom ash, process quench water and
leachate and/or ground water (when available) from mono-filled landfills
containing the solid residues. In addition, ground water samples from
any monitoring wells located near the landfills were to be characterized.
This project is intended to provide U.S. EPA's Office of Solid Waste
with preliminary data characterizing MWC residues in advance of similar
data to be provided in other studies underway or scheduled for initiation
in Fiscal Years 1987 and 1938.
1.3 Summary of Approach
This study was conducted in five Tasks briefly summarized below:
Taste 1: Preparation of Work Plan and Quality Assurance Project Plan
The Work Plan was prepared in accordance with the Scope of Work and
in consultation with the Project Officer, and approved August 15, 1986.
Following approval of the Work Plan, a Quality Assurance Project
Plan (QAPP) was prepared in accordance with the guidance for Category II
projects and with "Interim Guidelines and Specifications for Preparing
Quality Assurance Project Plans" (QAMS-005, December 29, 1980). The QAPP
was approved with recommendations on October 3, 1986. During the course
of the study, the QAPP was revised to respond to the recommendations made
in conjuction with the approval, and to recommendations made pursuant to
a Technical Systems Audit and an Audit of Data Quality conducted at
Versar on January 15, 1987. The final revised QAPP was submitted
February 3, 1987.
Task 2; Limited Literature Review
A review of the published literature on the characterization of MWC
residues was conducted. The scope of the review was limited to an
extension of more comprehensive reviews conducted previously and in
progress at the time of this study for the EPA Office of Solid Waste.
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The review was intended to (1) ensure that this study did not merely
duplicate the MWC characterization work of others, (2) provide data for
comparison with results of analyses obtained in this study, and (3) cover
portions of the published literature which other studies may not have
adequately examined.
Task 3; MWC Residue Sampling and Analysis
This task was conducted in six (6) Subtasks as described below.
EPA/HWERL assisted in identifying and assuring access to the MWC
facilities at which samples were collected.
Subtask 1 — Preliminary Survey of Facilities
The lead technicians for each of two sampling teams with the
supervision of the Project Manager and the Task Manager, made telephone
contact with personnel at MWC facilities identified in order to
(1) acquaint facility personnel with the objectives of the study,
(2) determine general operating characteristics of the facilities (type
of combustor, characteristics of wastes accepted, combustor operating
conditions, etc.), (3) determine locations for sampling solid residues,
field leachate and ground water, and (4) schedule dates for preliminary
site inspection and sampling. These telephone interviews also
established whether the facility met the selection criteria as discussed
in Section 3 of this report.
Subtask 2 — Initial Site Visit and Inspection
The lead technicians for each sampling team and the Task Manager
visited each of the four MWC facilities identified to obtain additional
detail on facility operation, locate points of access for collecting
residue samples, identify locations for sampling field leachate and
ground water (if any), and establish working relationships with facility
personnel.
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Subtask 3 — Sample Collection
Samples of MWC solid residue, field laachate, and ground water were
collected at sampling points identified in Subtask 2 above.
The lead technician and one addition sampling technician collected
the samples. Procedures for sample collection, preservation,
documentation, and shipment to the laboratory are described in detail in
Section 3 of this report.
The number of samples of each medium actually collected are
summarized in Table 1.1 below.
TABLE 1.1 SAMPLES COLLECTED FROM MWC FACILITIES
Liquid Samples
Solid Samples
Facility
A
B
C
0
(^•) Samples
A
B
C
D
Field
Leachate
0.
3
3
3
include
—
1
Ground
Water
1
1
4
0
Quench
Water
2
3
2
3
Bottom
Ash
6
6
7
6
Fly
Ash
7
6
9(3)
7
Landfill
Composite
1
1
the following duplicates
- —
—
1
1
1
1
2
1
2
1
1
2
,. —
Samples include one composite at each facility for preparation of
laboratory leachates, plus 3 composite duplicates.
Samples include grab samples of 3 different size fractions of
fly ash.
In addition, 4 trip blanks consisting of deionized water from the
Versar laboratory, carried to the facility, handled like a sample, and
returned for analysis were taken. And 2 field blanks consisting of
deionized water poured over and through the cleaned sampling devices and
returned for analysis were collected.
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Subtaak 4 — Sampla Analyses
Solid residue samples (fly ash and bottom ash) and liquid samples
(field leachate, ground water and quench water) and leachates prepared in
the laboratory from the solid residue samples were analyzed for various
heavy metals and organic compounds. The laboratory leachates were
prepared using the Extraction Procedure (EP), the Toxicity Characteristic
Leaching Procedure (TCLP), and the Mono-fill Waste Extraction Procedure
(as described in SW-924). Sequential extractions were performed using
the monofill waste extraction procedure. Total Organic Carbon (TOC)
analyses were performed on all field water samples (plus blanks) and on
the laboratory leachates prepared by the SW-924. Analyses for total
metals were performed on all field water samples, laboratory leachates,
and solid residue samples.
An organic scan was performed on field water samples and laboratory
leachates to determine whether organic compounds other than PCDDs, PCDFs,
and PCBs were present. Selected field water samples and laboratory
leachates were solvent extracted and the compounds present in each
fraction (acid and base/neutral) were identified and quantified by GC/MS
techniques (EPA Method 625). The selection of the field water samples
and laboratory leachates for extraction and GC/MS analysis was based
largely on the TOC concentrations.
Analyses for PCDDs and PCDFs were performed by the Battelle, Columbus
laboratory (Versar's subcontractor for these analyses) on all fly ash
samples and on selected bottom ash and field water samples. In addition,
analyses were performed on TCLP leachates of 8 ash samples. PCDD/PCDFs
were identified and quantified at the homolog level; the 2,3,7,3 tetra-
chlorodibenzo-dioxin isomer was quantified separately.
Analyses for PCBs were performed on all solid residue and field water
samples. No PCS analyses were performed on laboratory leachates. The
PCBs were identified and quantified at the homolog level rather than as
Arochlors.
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The numbers of analyses for each group of constituents in each
medium actually performed in this study are summarized in Table 1.2.
TABLE 1.2 NUMBERS OF ANALYSES PERFORMED
(Including duplicates, trip blanks and field blanks)
Field Liquid
Analyses Samples
TOC
Metals (2)
Organic Scan
Organic Constituents
PCS
PCDD/PCDF(6)
31
29(3)
24(3)
27
22
Laboratory
Leachates
20<1)
48
44
32
8<7)
Solid
Residues
42
45
43
(l>Total organic carbon (TOC) analyses not performed on laboratory
leachates prepared by the EP and TCLP procedures because acetic acid
is used for pH adjustment.
(2>Total metals include copper, chromium, cadmium, lead, arsenic,
selenium, mercury, iron, manganese, zinc, and nickel.
(^Duplicates and field blanks, but not trip blanks.
organic scan consists of extraction with Freon 113 and
quantification of total organics using an infrared spectrophotometer.
(5>No duplicates performed on the organic scan.
(^Analyses performed by subcontractor (Battalia Columbus Laboratories).
<7>PCDD/PCDF analyses of TCLP leachates, one from each solid residue
composite from each facility.
Subtask 5 — Analytical Data Management
The analytical data from the laboratory were entered into a computer
system (i.e., IBM-PC and Lotus 1-2-3 software) to generate data tables
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and graphs. Field data, that is information describing the MWC facility
design and operating conditions, were also entered into the data base.
The data were arranged by MWC facility and variable or chemical
constituent. In cases where data comparisons would be meaningful (e.g.,
to examine the differences between laboratory leachate and field water
sample analyses), the data were grouped together or graphs were prepared
thereby highlighting significant trends. The compilation of all
analytical data includes the presentation of all quality assurance/
quality control data (e.g., results form the analysis of replicates,
percent recoveries of spikes or surrogates).
Subtask 6 — Ongoing QA Review
The analytical and quality assurance/quality control procedures were
detailed in the QAPP for this project. Each of the analytical procedures
(e.g., typically CLP methods) employed include quality control measures
to evaluate the performance of the method on a continuing basis. These
performance criteria were evaluated as specified by the method by the
laboratory and project QA/QC officer, and any deficiencies were resolved
either through re-analysis of the sample or the application of
appropriate correction factors. In addition, replicate analyses were
performed on 25 percent of all samples tested. The results of the
replicate analyses, as well as the procedural performance checks (e.g.,
spike or surrogate recoveries), are presented in a separate section of
this report so that the information may be interpreted in terms of the
actual level of confidence of the data.
Task 4; Data Evaluation
As the analytical and quality control data became available, efforts
were directed toward reviewing the data and field notes and interpreting
the results. Based on EPA's concern regarding the environmentally safe
disposal of MWC residues, the following technical concerns were addressed
during the evaluation of the data:
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1. Recant data available in the literature suggests that toxic
constituents (e.g., metals, organics) may be present in solid
waste residues generated by MWC facilities. The data derived
from this study were used to further examine whether a problem
associated with the land disposal of MWC residues exists.
2. The results of the analyses of the field water samples and
laboratory leachates were compared to determine if any of the
laboratory leaching procedures accurately model the constituents
found in the field water samples.
3. At each MWC facility, operating data were collected to
characterize the combustion conditions which resulted in
production of the residues that were sampled. The results of the
chemical analyses of solid and liquid samples, and laboratory
leachates were examined with respect to the combustion conditions
to identify any significant correlations.
Task 5: Project Report and Summary Report Preparation
The project report (including draft and final) has been prepared by
the Versar technical specialists who were assigned as team leaders for
each facility sampled. Versar senior scientists contributed to and
reviewed the report to ensure that the overall project objectives are met
and that the final report is technically sound and complete.
The report includes:
• Results of the literature review.
• All analytical results and field observations.
• All quality assurance and quality control and data.
• An interpretation of the significance of the data in light of
current disposal practices for MWC wastes and the findings of
other groups working on MWC residues.
A Project Summary will be prepared, based on the draft report, to be
published by EPA and included in the EPA/600 series of Research and
Development Project Summaries.
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2.0 REVIEW OF PERTINENT LITERATURE
Versar performed a limited literature review to obtain pertinent
information from previous studies of municipal waste combustion (MWC).
This review focused on acquiring literature that contained MWC residue
characterization data. This acquired data was then used for a
comparative evaluation with the MWC residue characterization data
generated in this study (see Section 5.1).
The literature review was performed by using the following sources:
a database of abstracts on MWC ash literature compiled by the University
of Massachusetts; the Dialog computer user service, which is a
compilation of technical document abstracts that are accessed by
"keywords" (e.g., fly ash, bottom ash, municipal waste combustion,
leachate, etc.); and Versar's in-house technical documents. These
sources were used to obtain more than 250 abstracts from potentially
pertinent documents. Then, each of the abstracts was read to determine
whether the publication contained information warranting its
acquisition. Because the focus of the literature review was MWC residue
characterization data, the publications describing topics such as
incinerator design, landfill design, analytical techniques for
characterizing the residue, stock sampling and analysis, and residue
utilization were omitted from any further consideration.
After the review of the abstracts was completed, 78 documents were
identified as potential sources of MWC residue characterization data were
acquired. The identified documents are listed in Appendix A. Each of
these documents was scanned to extract data for metals, polychlorinated
biphenyls (PCBs), polychlorinated dibenzo-p-dioxins/polychlorinated
dibenzofurans (PCDD/PCDF), and organic constituents (i.e., base/neutral
and acid extractable semi-volatile compounds-BNAs) in solid samples
(e.g., fly ash and bottom ash), laboratory leachates prepared from these
solid samples, and field water samples (e.g., field leachate, quench
water, and ground water). This scan of the publications revealed an
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abundance of data for metals and PCDD/PCDF in solid samples, indicating
that the metal and PCDO/PCDF composition of the solid MWC residues has
been extensively studied. This information was extracted from the
publications and is summarized in Section 5.1 (see Tables 5.1 and 5.3).
A limited amount of data was also available for PC3s in solid samples;
metals in Extraction Procedure (EP), Toxicity Characteristic Leaching
Procedure (TCLP), and deionized water laboratory-prepared leachates; and
metals and BNAs in field water samples, including quench water and field
leachate. This information is also summarized in Section 5.1 (see
Tables 5.2, 5.4, 5.5, 5.6, 5.7, and 5.8). Finally, the reviewed
publications did not contain any data for PCDD/PCDFa and BNAs in
laboratory-prepared leachates, or for PC3s and PCDD/PCDFs in field water
samples, indicating that the previous studies did not address these
contaminant/matrix combinations.
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3.0 APPROACH TO STUDY
This section discusses in detail the approach employed in this
investigation. Section 3.1 describes the process of selecting the four
MWC facilities sampled including the selection criteria and the
identification and selection process. Section 3.2 provides a description
of each of the facilities selected including the design and operating
characteristics of the combustor units and pertinent characteristics of
the landfills into which the MWC residues are disposed. Section 3.3
details the sampling procedures, sampling locations and samples collected
at each facility. Section 3.4 describes the procedures used in the
laboratory for preparing leachates, and the procedures for analyses of
all samples and laboratory-prepared leachates.
3.1 Municipal Waste Combustor Facility Selection
Four MWC facilities were selected for residue chemical
characterization. These facilities were chosen to (1) represent MWC
facilities generally in design and operating features, (2) provide a
range of design and operating features such that any difference observed
in the chemical characteristics of the residues could possibly be
qualitatively related to design and operating features, and (3) provide
samples of landfill leachate generated exclusively from MWC residues
rather than from mixtures of MWC residues and other solid wastes.
3.1.1 Facility Selection Criteria
The four MWC facilities studies in this project were selected from a
larger group of facilities known to EPA/HWERL and EPA/OSW in accordance
with the following criteria:
1. Facility Types - Two facilities were to have resource (e.g.,
energy or material) recovery processes, and two were to be
operated solely for waste volume reduction.
2. Information Availability - Each facility was to be currently
active and was to have information available on the engineering
design, operating characteristics (e.g., times, temperatures,
refuse feedrate, etc.), raw waste characterization (e.g..
3-1
-------
amounts of industrial wastes accepted and approximate percentages
of paper, food, plastic, textiles, etc.), and relative amounts
. and disposition of the various MWC residues (e.g., fly ash,
bottom ash, quench water, etc.).
3. Landfill ing of Solid Residues - Each facility was to have
disposed of the MWC residues in a cell or landfill separate from
other solid or hazardous wastes.
4. Suitability of Sampling Locations - The MWC facility and the
landfill should be designed to permit the collection of discrete
samples of the individual residues (fly ash, bottom ash, quench
water).
5. State and Facility Cooperation - To ensure that the sampling and
information gathering efforts would be performed in an efficient
and timely manner without obstructions due to any policy or
regulatory enforcement issues, representatives of the cognizant
state regulatory agency and of the facility should be willing to
cooperate with EPA/HWERL and contractor personnel.
Criteria 2, 3, and 5 were considered absolute, i.e., no facility
would be selected that did not meet these three criteria. With respect
to Criterion 1, it was important that both resource recovery and volume
reduction facilities be studied, but the relative proportions of the two
types were flexible. In fact, among the four MWC facilities selected,
three were energy recovery facilities (one with a material recovery
process proceeding combustion) and one was a volume reduction facility.
With respect to Criterion 4. optimally separate samples of fly ash and
bottom ash should be collected. However, combined bottom and fly ash
samples were considered acceptable if a separate fly ash sample could be
collected and the approximate fraction of fly ash in the combined ash was
known.
Other desirable features of the MWC facilities included the
following:
• The landfill containing the mono-filled MWC residues should have
an operating leachate collection system from which samples of
field leachate could be collected. Alternatively, locations,
where leachate could be obtained should be available.
3-2
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• Monitoring wells from which ground water samples could be
collected should be located down gradient in a water-bearing zone
potentially affected by leachate from the landfill.
3.1.2 Identification and Selection Process
EPA/HWERL and EPA/OSW first identified the states which currently
require that MWC residues be disposed of in a separate cell or landfill.
This assured that any facility selected would have a monofill disposal
area rather than a landfill with co-disposed solid wastes and/or
hazardous wastes. EPA/HWERL subsequently contacted representatives of
the cognizant regulatory agencies within each state to (1) enlist their
cooperation in the project/ and (2) determine MWC facilities that might
meet the selection criteria. Subsequently, letters were sent to the
state regulatory agencies describing the objectives of the project,
presenting a timetable for facility selection and sample collection, and
formally requesting the state agency's assistance.
The state agencies agreeing to assist the project then contacted the
facilities to briefly describe the project and to enlist the cooperation
of facility representative. Upon receipt of notification that facilities
had been contacted and had agreed to cooperate in the project, letters
were sent from EPA/HWERL to the individual facilities describing the
objectives of the project, and proposing a schedule for initial telephone
interviews, site visits, and sample collection by Versar personnel.
Once agreement had been reached of the facility's cooperation in the
project, Versar personnel contacted facility representatives by telephone
and obtained specific detailed information on the combustor facility
design and operating characteristics including the feed waste materials,
ash handling system, residue disposal practices, characteristics of the -
disposal cell or landfill, and the availability of locations for sample
collection. A questionnaire was developed and used for guidance in
conducting these telephone interviews.
3-3
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The information obtained in the telephone interviews was used to
make the final selection of the four facilities to be sampled. Some
facilities initially considered were eliminated at this point.
Subsequently, the Versar lead sampling technician and the Task
Manager (or designee) visited the facility to determine exact sampling
locations and the working conditions to be encountered during sampling/
and to make final arrangements with facility personnel on sampling
schedule and any special assistance required during sampling. The
information obtained in these initial site visits was used to plan the
sampling activities/ including the sampling equipment and sample
containers required/ and the sampling strategy (e.g. time compositing
versus spatial compositing). The actual sampling was conducted within
three weeks of completion of the initial facility visits. Sampling
locations and procedures are described in detail for each facility in
Section 3.3.
3.1.3 Conformance to Selection Criteria
The degree to which each facility selected met the criteria for
selection is summarized in Table 3.1.
Among the four facilities, three were operated for energy recovery
with one (Facility A) having some limited capability for recovery of
aluminum from the feed prior to combustion. One facility was operated
for volume reduction only.
All four facilities provided detailed information on the combustor
design and operating characteristics and made available as much
information as they had on the design of the landfill receiving the solid
residues. At all four facilities/ the solid residues were disposed in
monofill landfills.
At three of the facilities/ bottom ash and fly ash were combined and
there was no feasible way to collect a separate bottom ash sample. At
all facilities, however, separate fly ash samples were collected.
3-4
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TABLE 3.1 FACILITY CONFORMANCE TO SELECTION CRITERIA
CRITERIA
i . Facility Types
2. Information Available
3. Monoflll Disposal
4. Sampling Locations
FACILITY
A
RR/ER
Yes
ves
Fly &
Combined
a
ER
Yes
Yes
Fly &
Bottom
c
VR
Yes
Yes
Fly &
Combined
D
ER
Yes
Yes
Fly &
Combined
5. State/Facility
Cooperation
Yes
Yes
Yes
Yes
Other:
• Leacnate Collection System No
• Monitoring wells 1
NO
1
NO
4
NO
0
RR » Resource Recovery; aluminum recovery oefore combustion.
ER = Energy Recovery as steam.
VR a volume Reduction only.
3-5
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Although some of the landfills associated with the facilities had
leachate collection systems in place, none were functioning as designed
at the time of sample collection for this scudy. Samples of field
leachate were collected at three of the facility landfills (B, C, and D)
at locations of opportunity as described later.
Suitably-placed monitoring wells were available and were sampled at
three of the facilities (A, B, and C).
Overall, the criteria for facility selection were achieved with
reasonable success in the four facilities selected. The two main areas
of deficiency with respect to the criteria were in the access to fly ash
and bottom ash separately in the ash processing line and the lack of
functioning leachate collection systems at landfills.
Further inquiry by Versar personnel has indicated that few combustor
designs provide access to fly ash and bottom ash separately. In the
limited time available to conduct the search for MWC facilities, it was
not possible to locate more than one such combustor.
A leachate collection system, which was present at only one facility
had apparently become clogged and was not draining. This may be a
pervasive problem with mono-filled disposal cells containing MWC residues
which have been in operation for more than a few years.
3.2 Facilities Selected
Based upon the selection criteria presented in Section 3.1.1 and the
involvement of EPA and appropriate state agencies, four facilities were
selected for MWC residue characterization sampling. Because each of the
facilities was assured that the source of the data for this study would
not be identified, the facilities were generically designated throughout
this report as Facility A, B, C, and D. After the facilities were
selected, they were contacted by telephone and visited prior to sampling,
to obtain operating and design characteristics of the incinerators and
3-5
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their associated landfills. Sections 3.2.1 through 3.2.5 present descrip-
tions and summary tables of these operating and design characteristics
for each facility.
3.2.1 Facility A
Facility A operates two water-wall rotary combustors which were put
on line in December 1981 and March 1982. Figure 3.1 presents a diagram
of a typical rotary combustor. The units are each rated at 100 tons per
day and operate 24 hours per day, 7 days per week. The total actual
operating capacity is about 150 to 180 tons per day, depending on the
moisture content of the feed. Each unit is equipped with a mechanical
cyclone separator and an electrostatic precipitator.
The units were originally the same, but Unit 2 has been retrofitted
to provide better air control. The majority of the air to Unit 1 is
overfire. Unit 2 was retrofitted to better control the percentage of
overfire and underfire air.
The units are monitored using televisions to maintain the fire in
the middle of the combustor area. In addition, oxygen, carbon monoxide,
furnace temperature, and residues are monitored to determine the
combustion efficiency. The feed rate and the amount of combustion air
are changed to control the combustion.
The feed to the units is approximately 50 percent residential and
50 percent industrial (i.e., construction type refuse including wood,
plastic, and metal). The facility has the ability to separate glass,
iron, and aluminum from the feed, but does not process all feed to the
combustors. From the refuse pit, the bucket feeds the two charging
hoppers (See Figure 3.1) to the combustors and the charging hopper to the
separation process. The processed feed is discharged back into the
refuse pit, where it is used to feed the combustor charging hoppers.
Occasionally, the refuse in the pit covers the inlet or the outlet of the
separation process making it impossible to process refuse. When refuse
3-7
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Figure 3.1 Facility A Combustor
BOIL2R
ROTARY COMflUSTOR
1 Charging Hopp«r
2 Charging Raa
3 Trunnion for Sarrtl Rocacion
4 Wind Box and A»h Removal
3 Uaecr Cooling Sysetfl Kocary Joint
4 Final Burnout Zon*
7 Primary A»h Oischargt Chutt
8 Aih Qu«nch Tank
CROSS-SECTION OP
ROTARY COMBUSTOR
3-8
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is processed, the aluminum is recycled, but the glass and iron are
disposed at the landfill along with the ash.
The residues from the combustors include bottom ash, fly ash, and
quench water. The units achieve approximately 90 percent reduction by
volume and 50 to 60 percent reduction by weight of -the incoming, refuse.
The bottom ash falls into a quench tank and is drag conveyed to a
temporary storage bin which has sufficient capacity to hold the ash
produced over 4 hours (i.e., 14 to 18 cubic yards). The fly ash, which
is removed from the flue gas using mechanical cyclone separators and
electrostatic precipitators, enters a turbulator where water is added.
The fly ash feeds to the quench tank displacing some quench water. The
displaced quench water (i.e., approximately 10 to 15 gallons per minute
total) overflows to a sump where solids are.removed The effluent from
the sump is discharged to the sanitary sewer. The bottom and fly ash,
along with non-combustible and large items (i.e., large metal items,
tires, wood palettes, furniture, etc.), are transported to a landfill a
total of about 12 times per day.
The landfill is located about 13 miles northwest of the facility.
It was used for municipal refuse until about early 1982 when the
combustors came on line. The landfill is now used for ash, separated
glass and iron, and large items. The ash has been segregated from the
municipal refuse. A small creek runs close to the landfill (i.e.,
200 yards). There is no leachate collection system, but there are two
ground-water monitoring wells in the new section of the landfill where
the ash is placed. The landfill is surrounded by a berm that limits the
release of surface runoff to adjacent areas. One monitoring well that is
closer to the older ash is reported to be frequently dry. The second
monitoring well, which contains water, is closer to the freshly placed
ash, but at quite a distance (i.e., 400 to 500 feet). The landfill is
covered daily with soil.
3-9
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3.2.2 Facility B
Facility B operates three water-wall traveling grate mass burn
combustors similar to the unit shown in Figure 3.2. Units 2 and 3 were
put on line in 1974. Unit 4 was put on line in September, 1986. Units 2
and 3 are each rated at 360 tons per day, and Unit 4 is rated at 400 tons
per day. The units operate 24 hours per day, 7 days per week. The total
actual operating capacity is about 600 to 700 tons per day, but will be
up to 900 tons per day when Unit 4 is completely operational. The feed
to the units is approximately 30 percent residential and 20 percent
commercial. Combustion efficiency is controlled by changing the amount
of underfire air to produce the required steam flow (i.e.,
30,000 Ibs/hour each unit). Each unit is equipped with a cyclone and an
electrostatic precipitator for participate control.
The residues include bottom ash, fly ash, and quench water. The
units achieve approximately 90 percent reduction by volume and 70 percent
reduction by weight of the incoming refuse. The bottom ash is spray
quenched (i.e.-, approximately 20 to 25 gallons per minute each unit),
stored in an enclosed hopper, and discharged into a disposal trailer (See
Figure 3.2) about every two hours (i.e., 3 to 4 hoppers of bottom ash per
combustor per shift). Each trailer has sufficient capacity to hold two
bottom ash dumps. Fly ash from each unit is removed from the flue gas
stream in separate cyclones and electrostatic precipitators, mechanically
conveyed (i.e., screw conveyors) to a combined duct, and discharged to an
enclosed storage bin through a large hose. The quench water is discharged
from the bottom ash hoppers, spills to the pavement below, and is
collected in a surface drain. The quench water is discharged to the
sanitary sewer after solids are removed in a sump.
The landfill is located about five miles east of the facility and
has been used for the disposal of bottom ash and fly ash for about 4 to
5 years. The landfill was estimated to be approximately 15 acres
(rectangular) in surface area and about 40 feet deep. The ash is
3-10
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Figure 3.2 Facility B Combustor
INCINERATOR SIDE VIEW
HEATING PLANT
I. C1ANI
2. CHANGING NCWH
3. SOUO WASTf COMPACTQI TtAIUI
4. «3U« UVU tKlMOCATINO O*ArU
i. SOUO WASTf STOIACI MT
4. raiCfD OlAfT FAN
7. ASH HOPPft
I. ASH OIS^OSAI TIAIIH
9. AUXIIIAIT IUINU
10. OUST COUKTOI
it. MKIWTATOI wwft surnr
12. ASM (CMOVAl STSHM
13. flfOnoSTAHC MK1P1TATOI
U. INOOCfO OlAfT ftM
15. STACK
14. KONOMIZtR
17. TOP Ol STtAM OIUM
II. SUPfl HfATfl
1*. LOWfl OIUM
20. raicio AII i NUT
3-11
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disposed of in 10 foot layers and covered with soil. A river is in
proximity to the landfill (i.e., approximately 100 yards). There is no
leachate collection system, but there are four ground-water monitoring
wells. Surface runoff is controlled with hay bales along the sides of
the landfill. The two wells closest to the active area of the landfill
are often dry. The two wells closest to the older portion of the
landfill contain water, but one well is at a very steep angle.
3.2.3 Facility C
The incinerator at Facility C includes two units, each consisting of
a reciprocating grate and a rotary kiln combustor. The incinerator was
brought on line in January 1970, and currently a third unit is being added
to the facility. The new unit will be equipped with a boiler and a
generator for energy recovery, and it should be operational by late 1986
or early 1987. If the new unit is efficient and cost effective, then the
existing units will be retrofitted with energy recovery systems in the
future. The two existing units are mass burn, volume reduction units
without resource recovery. Figure 3.3 presents a diagram of the
incinerator.
The existing units are identical, each having a rated capacity of
300 tons per day. The actual operating capacity for each unit is
approximately 250 tons per day. The units operate at approximately
1600°F to 1300°F, and no additional fuel is used for burning the refuse.
The units have a residence time for combustion of 30 to 45 minutes. Each
unit is equipped with a crude economizer to remove the coarse fly ash, a
cooling chamber to remove the medium fly ash, and an electrostatic
precipitator to remove the fine fly ash.
The units are monitored in the control room to ensure that optimum
combustion efficiency is maintained. The excess air, reciprocating grate
combustion chamber temperature, rotary kiln combustion temperature,
carbon monoxide, feed rate, and residue generation are monitored. The
feed rate and overfire air are continually adjusted to maintain efficient
operation.
3-12
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Op (1C I
momt
lorccd owtrhrc
droll x-air
ion Ian
rotary conveyers
(lo clurilier)
ESRcontrol
room
Figure 3.3 Facility C Combustor
-------
The feed to the units is approximately 50 percent residential and
50 percent industrial (i.e., paper, wood, plastics, and metals). The
facility does not process the waste before combustion, however, large
objects (e.g., tires, refrigerators, stoves, water heaters, etc.) are
removed by the feed crane operator, if noticed. The refuse is gravity
fed into the incinerators; it has a heating value of approximately 5000
BTU's per pound. Each unit burns approximately 75,000 tons of raw trasn .
per year.
The residues from the combustors include bottom ash, fly ash, and
quench water. The units achieve a volume reduction of 90 percent and a
weight reduction of 70 percent over the raw refuse. The bottom ash falls
into a quench water tank and is transported to a temporary storage bin by
a drag conveyor. The fly ash is transported by a screw conveyor and a
trough to the quench water tank, where it is removed with the bottom
ash. The displaced quench water overflows into a settling tank, where
the solids are removed. The clarified quench water overflows a weir at
the end of the settling tank into a wet well (i.e., sump),.and then
discharges to the local wastewater treatment plant. "The bottom ash, fly
ash, and materials removed prior to combustion are trucked to the on-site
landfill for disposal.
The landfill is constructed as a series of hills and valleys, where
the natural valleys are being filled with the combustion residues. The
landfill has been used since 1970, and is expected to be used until the
year 2050. There is no leachate collection system, however, there is a
seep where field leachate may be collected. The landfill is situated
very close to two streams. The one stream is fairly small, and the
landfill actually extends over top of the stream with a culvert beneath
it. The other stream is a major river approximately 300 yards away from
the landfill. There are three monitoring wells and a production well
located in between the landfill and river. On a daily basis, waste is
disposed by dumping the loads of residue on top, and then pushing the
fresh loads down the sides with a bulldozer.
3-14
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3.2.4 Facility D
The Facility 0 incinerator consists of two identical water-wall
traveling grate mass burn combustors similar to the unit depicted in
Figure 3.4. The facility's construction began in December 1969, and the
facility began operating in October 1972. The units are rated at 360 tons
per day each, however, the actual operating capacity is approximately
310 tons per day for each unit. However, if the refuse feed is less than
5000 Btu's per pound, the feed rate is slowed to allow for longer
residence times and more complete combustion. The units operate 24 hours
per day, 7 days per week, 50 weeks per year, with approximately 2 weeks
per year for maintenance. The units typically operate at approximately
1500 F, and no additional fuel is used for the combustion. The
residence times within the units range from 4 to 5 hours with the longer
residence times necessary for wet feed refuse. The units are equipped
with economizers and electrostatic precipitators for removing fly ash.
Steam is generated by the progressive cooling of the furnace gases by the
welded-membrane water-cooled walls of the combustion chamber, and by the
five passes of the hot gases through the convection and generating
sections of the boiler. Each boiler has a continuous steam generating
capacity of 92,500 Ibs/hr.
The units are monitored from a control room using television
monitors and operating variables. The combustion temperature, oxygen,
feed rate, and residue generation are all monitored. Presently, the
combustion temperature is the major operational variable, however, the
facility is switching to an oxygen monitoring system which was
demonstrated to yield more efficient operation.
The feed to the units is approximately 50 percent residential and
50 percent industrial (e.g., wood, paper, plastics, metals, etc.).
Additionally, in 1985 an automatad sludge disposal system was added to
permit the facility to incinerate sludge from the nearby wastewater
treatment plant. The sludge is mixed with the refuse, and the feed rate
3-15
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1
u>
t->
o\
i;«
i'1
•1
ID
CJ
n
n
I
£
-------
is controlled to maintain a combustion temperature of 1400°F to 1500*F.
The facility does not process the waste prior to combustion, except that
tires are removed and shredded before being burned. However/ large
noncombustible items (e.g./ refrigerators/ water heaters, etc.) are
removed and sold for scrap metal.
The residues from the facility include bottom ash, fly ash, and
quench water. The units achieve a volume reduction of 35 percent, not
including the large materials removed before combustion. Bottom ash
falls into a quench water tank and is transported by a conveyor belt to a
temporary storage bin. Fly ash, which is removed by the economizer,
drops down a chute into the quench water tank. The electrostatic
precipitator ash is transported by a screw conveyor to the chute, where
it joins the economizer ash and is subsequently gravity fed to the quench
water tank. The quench water is removed with the ash, and the overflow
is collected in a drain and routed to the wastewater treatment plant.
Trucks transport the bottom ash, fly ash, and associated quench
water to the on-site landfill. The landfill is a tall mound located on a
square area (approximately 500' x 500'}. It has been in use for several
years and is now overflowing. The landfill has a leachate collection
system, however, the system is obstructed so leachate cannot be collected
from this system. The facility does not have any ground water monitoring
wells; it is only approximately one mile east of a major river.
3.2.5 Summary of Facility Design and Operating Characteristics
Several differences and similarities, which may contribute to the
residue characteristics, were observed in the facility descriptions (see
Sections 3.2.1. through 3.2.5) and are highlighted in this section. All
four incinerators are less than 20 years old with capacities ranging from
200 tons per day (tpd) to 1120 tpd. One of the incinerators is
relatively small (Facility A-200 tpd), while the other three are of
medium size (600-1120 tpd). Two of the incinerators are traveling or
reciprocating grate designs (Facilities 3 and D); the third is a rotary
3-17
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kiln design (Facility A); and the fourth is a combination of these two
designs (i.e., reciprocating grate and rotary kiln in series for
Facility C). Large metal objects (e.g., water heaters, refrigerators,
etc.) and tires are removed at each incinerator prior to combustion,
while only one incinerator (Facility A) processes its waste to remove
iron, aluminum, and .glass. All four incinerators are equipped with
electrostatic precipitatocs to remove flue gas particulates, and two of
the incinerators (Facilities A and B) are also equipped with cyclones to
remove additional fly ash particles. A summary of the design and
operating characteristics is presented in Taole 3.2
The landfill for each facility is more than five years old and is a
monofill with only combustion residues and non-combustibles, including.
tires, disposed. Three of the landfills (Facilities B, C, and 0) are not
adequately lined or capped, and therefore, they would be expected to
produce and release leachates. This is potentially a problem because the
landfills are generally close to the water table (<30 feet) and are in
proximity to surface water. .The fourth landfill (Facility A) is lined
and capped with clay, and therefore, does not pose a significant leachate
problem. Three of the landfills are near capacity and are expected to
close by early 1987 (Facilities A, B, and D), while the fourth landfill
is expected to be used for at least 60 aore years. Table 3.3 presents a
summary of the landfill characteristics.
3.3 Samples and Sampling Procedures
In order to meet the objectives of this study, Versar's personnel
collected MWC residue samples and field water samples from the four
facilities described in Section 3.2. These samples were collected
between September 26 and October 22, 1936, and although the sampling
locations and techniques were facility specific, the samples from each
facility typically included: bottom or combined ash, fly ash, quench
water, ground water, and field leachate. Additionally, composite samples
of the fly and bottom ashes were collected for laboratory extraction
3-13
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TABLE 3.2 MUNICIPAL WASTE COMBUSTOR DESIGN AND OPERATING CHARACTERISTICS
Characteristic
Facility A
Facility B
Facility C
Fac-ility 0
Hunter of Combustors
Designation of Each Combustor
Year of Construction
Energy Recovery System
Type of Combustor
Capacity (tons/day)
o Design
o Operating
Operating Schedule
Hours/day (days/week)
sign Combustion Temperature (F)
Residence Tim (hours)
Air Pollution Control System
2
n/tz
1981/1962
Yes
Continuous Feed
Water-wall
Rotary K1ln
100/100
75-90/75-90
24 (7)
1200
0.75
Cyclone, ESP
3
»2/f3/*4
1974/1974/1986
Yes
Continuous Feed
Water-wall
Traveling Grate
360/360/400
275/275/300
24 (7)
1300
0.75
Cyclone, ESP
2
»!/«
1970/1970
No
Continuous Feed
Reciprocating Grate
Rotary Kiln
300/300
250/250
24 (7)
1800
0.5 - 0.75
ESP
2
ll/»2
1972/1972
Yes
Continuous Feed
Water-wall
Reciprocating Grate
360/360
310/310
24 (7)
1400-1500
4 - 5
ESP
Bottom Ash Handling System
Fly Ash Handling System
Quench Water Flow (gal/day)
Quench Water Disposal
Waste Composition (*)
o Residential
o Cornnerdal/Industrla!
Waste Processing or Pre-handling
Wet (Quench Tank) Wet (Quench Tank)
Wet (Quench Tank) Dry
17,000 35,000
POTV POTW
Wet (Quench Tank) Wet (Quench Tank)
wet (Quench Tank) Wet (Quench Tank)
23,000 23,000
POTW POTW
50
50
Remove large
objects; separate
glass, iron, and
aluminum for recyle
80
20
Remove large
appliances and
tires
50
50
50
50
Refuse Storage Location and Capacity Piled in pit; Piled in pit;
two-day capacity two-day capacity
Large iten Remove tires and
removed by crane large noncombustible
operator materials: recycle
ferrous metals as
scrap; periodically
shred and burn tires
Piled in pit; Piled in pit;
two-day capacity two-day capacity
3-19
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TABLE 3.3 LANDFILL CHARACTERISTICS
Characteristic
Amount of Combostor Residue Disposed
(tons/day)
Other Types of Waste Disposed
Facility A
Facility 8
Facility C
Facility 0
Year Landfill Began Operation
Projected Year Landfill Reaches Capacity
Shape
Lateral Dimensions (feet)
Depth Below Grade (feet)
Maximum Height Above Grade (feet)
Slope
Portion of Landfill That is Capped (%)
Cap Material and Thickness
Leachate Collection System
Runoff Control Measures
60
Tires, large items.
construction
debris and.
noconbustibles
1982
1987
Rectangular
500 x 1. 000
<10
35 - 40
Relatively flat
with sloping
sides
90
Clay
3 feet
None
Impermeable cap;
graded contour;
diversion ditch
around landfill
perimeter
120
Large items and
construction debris
1981
1987
Rectangular
500 x I. 000
20
20
Relatively flat
with sloping
sides
90
Native soil
6-12 inches
None
Relatively thin
cap; hay bales
around one corner
of landfill to
inhibit runoff
155
Nonconbustlble
items
1970
2050
Rectangular
(multiple mounds
on hilly terrain)
300 x 1,500
0
60
Hilly terrain
with numerous
waste mounds
0
NA
None
Adjacent mounds
of waste tend
to trap surface
water; erosion of
slope evident
90
Tires and
noncombustibles
Post 1980
1987
Square
500 x 500
20
50
Single mound of
waste with steeply
sloped sides
0
NA
Gravel
(not functioning)
Flat area adjacent
to waste pi 1e
tended to collect
surface water
Depth to Ground water (feet)
Number of Monitoring Wells
Distance to Nearest Domestic Well
Distance to Nearest Surface water
15
10 - 15
2 (one useable) 4 (two useable)
> 1/4 mile < 500 feet
200 fett
(small stream)
200 feet
(major river)
30
1,000 - 1.500 feet
1,000 fMt
(major river)
>100
> 1/4 mile
1 mile
(major river)
3-20
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using three different leaching procedures (i.e./ Extraction Procedure,
Toxicity Characteristic Leaching Procedure, and Mono-filled Waste
Extraction Procedure). Where available, samples of disposed ash and
discrete fly ash fractions were also collected to more adequately
characterize the MWC residues and the environmental effects of their
disposal. The following sections (See Sections 3.3.1 through 3.3.4) will
describe, in detail, the samples, sampling locations, and sampling
procedures for each of the four facilities.
3.3.1 Facility A
Versar personnel collected groundwater samples at Facility A's
landfill on September 25, 1986 and MWC residue samples at Facility A on
September 26, 1986. The MWC residue samples included: bottom/fly ash
(i.e., a mixture of bottom ash and fly ash), fly ash, and quench water.
As per sampling plan specifications, 25 percent of the samples were
collected in duplicate for quality control (QC).
The MWC residue sampling at Facility A commenced at the beginning of
the second shift (i.e., 7:00 a.m. to 3:00 p.m.) on Friday, September 26,
1986, and was completed at the end of the third shift (i.e., 3:00 p.m. to
11:00 p.m.) on Friday, September 26, 1986.
Units 1 and 2 were sampled separately to determine if any
differences exist in the characteristics of the residues due to the
independent operating parameters for each system.
Although the landfill at Facility A did not have a leachate
collection system, the Versar monitoring team explored the perimeter of
the landfill to find a natural seep for leachate collection. Such a
location did not exist, so no field leachate samples were collected.
However, at the request of EPA/HWERL, a follow-up visit was scheduled for
October 22, 1986, to again attempt to collect a field leachate sample.
Although the follow-up visit was scheduled after a period of heavy rain,
the landfill perimeter was still dry with no natural seeps. Therefore,
no field leachate samples could be obtained at Facility A.
3-21
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While the samples were being collected, the combustor operator
recorded pertinent operating data to be used for evaluating contaminant
concentration differences between units, shifts, and facilities (See
Section 5.0). This operating data is shown in Section 4.1, Table 4.1.
Table 3.4 presents a summary, including field sample numbers, of the
samples collected at this facility. Detailed descriptions of the
sampling locations and procedures for each of the sample matricies are
presented below.
Groundwater - The groundwater samples were grab samples collected
the afternoon of September 25, 1986. There are two groundwater
monitoring wells in the section of the landfill near where the ash is
placed. One monitoring well that is closer to the older ash was dry.
The second monitoring well which is closer to the freshly placed ash, is
on a hillside approximately 400 to 500 feet from the active part of the
landfill and contained water.
Prior to sampling the groundwater in the second monitoring well, the
volume of standing water in the well casing and saturated annulus was
determined by measuring and recording the well casing diameter, the depth
from the top of the well casing to the water surface, and the depth from
the top of the well casing to the sediment/water interface. The volume
of standing water was approximately 0.3 gallons.
Because of the small volume of water and the reported slow
recharging rate, the monitoring well was not evacuated. Instead, grab
samples were collected from the standing water using a Teflon bailer.
The water was clear with no visible particulate matter; therefore, the
samples were not filtered. The clean, labeled sample containers (i.e.,
4-oz. glass for TOG, 1-L glass for organic scan, 1-L plastic for metals,
and one and a half 1-L glass for PCDO/PCDF) were filled directly from the
Teflon bailer, documented on chain-of-custody forms, packed on ice in an
Igloo-type cooler, and shipped to the laboratory by priority air express.
The coolers were secured with EPA custody seals.
3-22
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TABLE 3.4 SAMPLE IDENTIFICATION COOES FOR FACILITY A
Sample
Matrix
Blank
Sample
Description
Trip Blank
Bottom/Fly Composite
Bottom/Fly Unit 1, 9/26, AN
Bottom/Fly Unit 1. 9/26, PN
Bottom/Fly Unit 2. 9/26, AN
Bottom/Fly Unit 2. 9/26. AM, Oup
Bottom/Fly Unit 2, 9/26. PN
Fly Composite
Fly Composite, Oup
Fly Unit 1, 9/26, AN
Fly Unit 1. 9/26, AN, Oup
Fly Unit I. 9/26, PN
Fly Unit 2. 9/26, AN
Fly Unit 2. 9/26, PN
MHell II
Quench Unit 1, 9/26
Quench Unit 2, 9/26
Organic
TOC Scan Metals SNA PCS
No. No. No. No. No.
17652 17653 17650 17654-57 17662-63
17626 17625
17639 17640
17618 17619
17621 17622
17633 17634
17627 17628
17630 17631
17636 . 17637
17642 17643
17645 17646
18363 17506 18370
18362 17504 17501 17538-41 17546-47
18375 17505 18369 17548-51 17556-57
PCOO/
PCOF
No.
Lab
Leachate
No.
17658
17624
17641
17620
17623"
17635
17629
17632
17638
17644
17647
17523-24-
17542-45
17552-55
17651
17648
17649
LEGEND:
Bottom/Fly - Combined bottom ash and fly ash samples
Fly • Fly ash
MHell • Groundmter from monitoring well
Quench • Incinerator quench water
TOC - Total organic carton
SNA • Base/neutral acid extractable organic*
* • Sample collected but not analyzed
3-23
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Bottom/fly ash - The Versar monitoring team collected a combined ash
(i.e., a mixture of-bottom ash and fly ash) sample rather than a bottom
ash sample because a location where a discrete bottom ash sample could be
collected was not available. Each bottom/fly ash sample was a
time-composite composed of eight grab samples representing each
combustor/shift combination (i.e.. Unit 1 or Unit 2, 2nd shift or 3rd
shift).
During the 2nd shift, the grab sample portion of the time-composite
sample was collected every hour over an eight-hour period. Unit 1 was
having a clinker problem and Unit 2 was naming raw refuse. The fourth
grab sample from Unit 2 was collected after a 1-1/2 hour interval rather
than a 1-hour interval because the drag conveyor had been shut off. The
seventh grab sample from both units was collected after a 2-hour interval
during which the Unit 2 conveyor had been shut off for about an hour.
During the 3rd shift, sample increments were collected every 45 minutes
over a five and one half-hour period. At the beginning of shift 3,
Unit 1 was burning hot and the bottom ash on the conveyor was on fire/-
therefore. Unit 1 was not sampled for the first three grabs and the
volume of the last five grabs was doubled. Unit 2 was still running
cold. Per sampling plan requirements, the time-composite collected from
Unit 2 during the second shift was split for field and laboratory control.
Each bottom/fly ash grab sample was collected from the quench tank
drag conveyor of each unit. The drag conveyor transports the ash from
the quench tank up an incline to a storage bin. As the ash is conveyer
up the incline, the quench water returns down the slope to the quench
tank. The bottom/fly ash is wet and contains uncombusted material (e.g.,
glass, cans, and metal scraps).
Each sample increment of the time-composite sample was collected by
stopping the drag conveyor and by taking a stopped-belt cut (ASTM
Method D2234-76) across the conveyor using a steel shovel. The cut was
perpendicular to the conveyor direction and was the width of the shovel.
The sides of the cut were as nearly parallel as possible to prevent
3-24
-------
particle-size bias. The incremental sample was placed in a polyethylene
lined three-gallon collection bucket and was thoroughly mixed with a
steel hand trowel. A 550-milliliter subsarcple (1,100 milliliters for the
sample to be split) was transferred to a lined compositing bucket. Large
pieces of uncombusted material were not included in the samples to
prevent sample bias.
At the end of the sampling period, the material in the compositing
bucket was thoroughly mixed with a hand trowel. The time-composite
sample was placed into clean, labeled sample containers (i.e., one
1-quart glass wide-mouth jar each for PCDD/PCDF, PCS, and metals) using a
steel hand trowel. In addition, the polyethylene bottle used to measure
the 550-milliliter aliquots was filled to obtain the bottom/fly ash
composite sample for laboratory leachate testing. The laboratory
leachate composite was prepared such that it is representative of both
combustors and both shifts of operation during which sampling was
performed. The samples were documented on chain-of-custody forms, packed
in Igloo-type coolers without ice, and shipped to the laboratory by
priority air express. The coolers were sealed with EPA custody seals.
Fly ash - Similar to the bottom/fly ash samples, four time composite
fly ash samples were collected composed of eight grab samples each
representing each combustor/shift combination (i.e.. Unit 1 or Unit 2,
2nd shift or 3rd shift). The fly ash samples were taken at the same
frequencies as the bottom/fly ash samples during the 2nd and 3rd shifts.
The volume of the fourth grab sample from Unit 2 was half the usual
amount, because Unit 2 was running cold. Per sampling plan requirements,
the fly ash time-composite collected from Unit 1 during the 2nd shift was
split for field and laboratory quality control.
Each fly ash grab sample from Unit 1 was collected from a screw
conveyor and each fly ash grab sample from Unit 2 was collected at the
inlet to a turbulator. For each unit, screw conveyors transport the fly
ash from separate cyclone separators and electrostatic precipitators to
3-25
-------
turbulators where water is added. The fly ash slurry feeds to the quench
tank displacing some quench water.
The grab samples from Unit 1 were collected by placing a steel hand
trowel under the discharge of the screw conveyor and collecting a full-
stream cut (ASTM Method D2234-76). The full-stream cut was collected by
placing the steel hand trowel under tr.e screw conveyor discharge, allowing
it to fill up, transferring the material to a polyethylene lined three-
gallon bucket and repeating several times until sufficient material was
collected.
The grab samples from Unit 2 were collected by placing a steel hand
trowel under the inlet of the turbulator. The part-stream cut (ASTM
Method 02234-76) was collected by placing the steel hand trowel under the
turbulator inlet, allowing it to fill up, transferring the material to a
polyethylene lined three-gallon bucket, and repeating several times until
sufficient material was collected.
After each grab sample was collected, the sample was thoroughly
mixed with the steel hand trowel, and a 550-milllliter aliquot
(1100-milliliters for samples to be split) measured into a polyethylene
bottle and poured into a covered and lined 3-galIon compositing bucket
until the end of the shift.
At the end of the compositing period, the material in the
compositing bucket was homogenized identically to the bottom/fly ash and
placed into clean, labeled sample containers (i.e., one 1-quart glass
wide-mouth jar each for PCDD/PCDF, PCB, and metals). In addition, the
polyethylene bottle used to measure the 550 milliliter aliquots was
filled to obtain the fly ash composite sample for laboratory leachate
testing. The laboratory leachate composite was prepared such that it is
representative of both combustors and both shifts of operation during
which sampling was performed. Per sampling plan requirements, the
laboratory leachate was split for field and laboratory control. The
samples were documented on chain-of-custody forms, packed in Igloo-type
3-26
-------
coolers without ice, and shipped to the laboratory by priority air
express. The coolers were secured with EPA custody seals.
Quench water - The quench water samples were grab samples
representing one combustor (i.e.. Unit 1 or Unit 2). The samples were
collected during the second shift (i.e.. Unit 1 quench water collected
about half way through the shift and Unit 2 quench water collected
towards the end of the shift). This being the case, these samples were
not representative of the entire shift, but only the instant in time at
which they were collected. Therefore, any time dependent variability of
the quench water contaminant concentrations was not accounted for in
these samples.
The quench water samples were collected in the tank. The fly ash
slurry from the turbulator feeds to the quench tank displacing some
quench water. The displaced quench water overflows to a sump where
solids are removed. The effluent from the sump is discharged to the
sanitary sewer. The quench water samples were collected in the tank
rather than at the sump overflow because the sump overflow was not
accessible.
The quench water grab samples were collected using a clean sample
container (i.e., 4-oz. glass for TOG, 1-L polyethylene for metals,
1-L glass for organic scan, four 1-L glass for base/neutral/acid, two
1-L glass for PCB, and four 1-L glass for PCDD/PCDF). The samples were
treated with the appropriate preservative (i.e., sulfuric acid for TOC
and organic scan, and nitric acid for metals), documented on chain-of-
custody forms, packed on ice in Igloo-type coolers, and shipped to the
laboratory by priority air express. The coolers were secured with EPA
custody seals.
3.3.2 Facility B
Versar personnel collected groundwater samples at Facility B's
landfill on September 27, 1986, and MWC residue samples at Facility B on
September 28 and 29, 1986. The MWC residue samples included: bottom
3-27
-------
ash, fly ash, and quench water. Per sampling plan, 25 percent of the
samples were collected in duplicate for quality control (QC).
The MWC residue sampling at Facility B was performed during the
second shift (i.e., 7:00 a.m. to 3:00 p.m.) on Sunday, September 23, 1986
and the third shift (i.e., 3:00 p.m. to 11:00 p.m.) on Monday,
September 29, 1986. The reason for the length of time between each
sampling shift was to determine if any differences exist in the
characteristics of the residues due to the length of time the refuse has
been in the incoming refuse collection pit. During sampling, Unit 2 was
down for maintenance; therefore, all MWC residue samples were collected
from combustion Units 3 and 4. Units 3 and 4 were sampled separately to
determine if any differences exist in the characteristics of the residues
due to different operating parameters and incinerator design features.
Although the Versar monitoring team also attempted to collect a
field leachate sample, no natural leachate seeps were available for
collection. However, at the request of EPA/HWESL, a follow-up visit was
scheduled for October 22, 1986, to attempt collection of a field leachate
sample. The follow-up visit was scheduled after periods of heavy rain;
therefore, Versar personnel were able to collect three field leachate
samples during this visit.
While the samples were being collected, the combustor operator
recorded pertinent operating data to be used for evaluating contaminant
concentration differences between units, shifts, and facilities (See
Section 5.0). This operating data is shown in Second 4.1, Table 4.2.
Table 3.5 presents a summary, including field sample numbers, of the
samples collected at this facility. Detailed descriptions of the
sampling locations and procedures for each of the sample matricies are
presented below.
Groundwater - The groundwater samples were grab samples collected
the afternoon of September 27, 1986. There are four groundwatar
monitoring walls at the landfill. The two wells closest to the active
3-28
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TABLE 3.5 SAMPLE IDENTIFICATION COOES FOR FACILITY B
Sample
Matrix
Blank
Bottom
Bottom
Bottom
Bottom
Bottom
Bottom
Fly .
Fly
Fly
Fly
Fly
Fly
Leachate
leactiate
Leachate
MWell
Quench
Quench
Quench
Sample
Description
Trip Blank
Composite
Unit 3. 9/28. AH
Unit 3, 9/29, PM
Unit 4. 9/28, AM
Unit 4, 9/28, AM, Oup
Unit 4. 9/29. PM
Composite
Unit 3, 9/28, AM
Unit 3, 9/28, AM, Oup
Unit 3, 9/29, PM
Unit 4, 9/28, AM
Unit 4, 9/29, PM
East Side
North Side
Northeast Corner
12
Unit 3. 9/28
Unit 4, 9/28
Unit 4, 9/28, Oup
Organic
TOC Scan Metals SNA PCS
No. NO. NO. No. Ho.
PCOO/ Lab
PCOF Leachate
No. No.
17696 17698 17697 17699-02 11703-04 17705-08
17694
19830
19856
19843
18367
18376
18377
18364
19832
19858
19845
17512
17S09
17510
17508
17664
17688
17673
17676
17682
17667
17670
17691
17679
17685
19831
19857
19844
18373
17502
17503
18371
19833-36
19861-64
19848-51
17579-80-
17588-91
17598-01
17528-31
17666
17690
17674
17677
17683
17669
17672
17693
17680
17686
19837-38
19859-60
19846-47
17596-97
17606-07
17536-37
17665
17689
17675
17678
17684
17668
17671
17692
17681
17687
19839-42
19865-68
19852-55
17582-85*
17592-95*
17602-05
17532-35
17695
LEGEND:
8otto» • Bottom ash
Fly - Fly ash
MMtll • Groundwater from monitoring well
Quench • Incinerator quench water
TOC • Total organic carbon
SNA « Base/neutral add ax tractable organlcs
* • Samples collected but not analyzed
3-29
-------
area of the landfill were in poor condition (one had been damaged by a
vehicle) and were dry. The two wells closest to the older portion of the
landfill contained water, but one well casing was at a very steep angle
and an accurate reading could not be obtained for the depth of the water
surface.
Prior to sampling the groundwater in the one remaining well, the
volume of standing water in the well casing and saturated annulus was
determined by measuring and recording the well casing diameter, the depth
from the top of the well casing to the water surface, and the depth from
the top of the well casing to the sediment/water interface. The volume
of standing water was approximately 2.6 gallons.
Because of the small volume of water and uncertainty on the
recharging rate, the monitoring well was not evacuated. Instead, grab
samples were collected from the standing water using Teflon bailers. The
water was clear with no visible particulate matter; therefore, the
samples were not filtered. The clean labeled sample containers (i.e.,
4-oz. glass for TOC, 1-L polyethylene for metals, 1-L glass for organic
scan, one and three quarter 1-L glass for base/neutral/acid, a-nd four
1-L glass for PCDO/PCDF) were filled directly from the Teflon bailer,
documented on chain-of-custody forms, packed on ice in an Igloo-type
cooler, and shipped to the laboratory by priority air express. The
coolers were sealed with EPA custody seals.
The Versar monitoring team returned to the Facility B landfill on
September 28, 1986, to determine how well the monitoring well recharged.
Unfortunately, the volume of standing water had not increased
significantly, so no more samples were taken.
Bottom ash - The bottom ash samples were composite samples composed
of four grab samples representing each combustor/shift combination (i.e..
Unit 3 or Unit 4, 2nd shift on September 28, 1986 or 3rd shift on
September 29, 1986). Unit 4 was running below optimum temperature during
the beginning of the third shift on September 29, 1986. A grab sample
3-30
-------
portion of the composite was collected each time bottom ash was
transferred to a dump truck during the shift. Per sampling plan
requirements, the composite collected from Unit 4 during the second shift
on September 29, 1986 was split for field and laboratory quality control.
Each bottom ash grab sample was collected from a disposal trailer.
The bottom ash is spray quenched, stored in an enclosed hopper, and
discharged into a disposal trailer about every two hours. Each trailer
has sufficient capacity to hold two bottom ash dumps. During the
sampling visit. Unit 3 was dumped in the back half of the trailer and
Unit 4 was dumped in the front half.
The grab sample portion of the composite sample was collected by
climbing up on the trailer and scooping with a steel hand trowel several
aliquots of ash from the freshly dumped mound and placing the material in
a polyethylene lined three-gallon collection bucket. The sample was
thoroughly mixed with the steel hand trowel, and a 1-quart aliquot
(2-quart for the sample to be split) was transferred into a polyethylene
covered and lined 3-gallon compositing bucket until the end of the
shift. Large pieces of uncombusted material were not included in the
samples to prevent sample bias.
At the end of the sampling period, the material in the compositing
bucket was thoroughly mixed with a hand trowel. The composite sample was
placed into clean, labeled sample containers (i.e., one 1-quart glass
wide-mouth jar each for PCDD/PCDF, PCB, and metals (using a steel hand
trowel. The polyethylene bottle used to measure the 1-quart aliquots was
filled to obtain the bottom ash composite sample for laboratory leachate
testing. The laboratory leachate composite was prepared such that it is
representative of both combustors and both shifts of operation during
which sampling was performed. The samples were documented on chain-of-
custody forms, packed in Igloo-type coolers without ice, and shipped to
the laboratory by priority air express. The coolers were sealed with EPA
custody seals.
3-31
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Fly ash - Similar to the bottom ash samples, the fly ash samples
were composites composed of four grab samples representing each combustor/
shift combination (i.e.. Unit 3 or Unit 4, 2nd shift on September 28,
1986, or 3rd shift on September 29, 1986). An incremental sample portion
of the composite was collected at times corresponding to periods when
bottom ash was dumped during the shift. Per sampling plan requirements,
the composite collected from Unit 3 during the second shift on September
29, 1986, was split for field and laboratory quality control.
Each fly ash grab sample was collected from a screw conveyor. The
fly ash from each unit is removed from the flue gas stream in separate
cyclones and electrostatic precipitators, mechanically conveyed (i.e.,
screw conveyors) to a combined duct, and discharged to an enclosed
storage bin through a large hose.
The grab samples were collected by turning the screw conveyor off,
removing the screw conveyor cover, and collecting the exposed material
with a gloved hand. The collected material was placed in a polyethylene
lined three-gallon bucket.
After each grab sample was collected, the sample was thoroughly mixed
with the steel hand trowel, and a 1-quart aliquot (2-quart for a sample
to be split) transferred to a polyethylene bottle and poured into a
polyethylene covered and lined 3-gallon compositing bucket until the end
of the shift.
At the end of the compositing period, the material in the compositing
bucket was homogenized and placed into clean, labeled sample containers
(i.e., one 1-quart glass wide-mouth jar each for PCDD/PCDF, PCS, and
metals). In addition, the polyethylene bottle used to measure the
1-quart aliquots was filled to obtain the fly ash composite sample for
laboratory leachate testing. The laboratory leachate composite was
prepared such that it is representative of both combustors and both
shifts of operation during which sampling was performed. The samples
were documented on chain-of-custody forms, packed in Igloo-type coolers
3-32
-------
without ice, and shipped to the laboratory by priority air express. The
coolers were sealed with EPA custody seals. •
Quench water - The quench water samples were grab samples
representing one combustor (i.e.. Unit 3 or Unit 4). The samples were
collected during the second shift on September 23, 1986 (i.e.. Unit 4
quench water collected at the beginning of the shift and Unit 3 quench
water collected about half way through the shift). This being the case,
these samples were not representative of the entire shift, but only the
instant in time at which they were collected. Therefore, any time
dependent variability of the quench water contaminant concentrations was
not accounted for in these samples. Per sampling plan requirements, the
grab samples for Unit 4 were split for field and laboratory quality
control.
The quench water grab samples were collected below the bottom ash
clamshell load-out hoppers. The bottom ash is spray quenched and stored
in an enclosed hopper. Quench water drains from the bottom ash hoppers,
spills to the pavement below, and is collected in a surface drain. The
quench water is discharged to the sanitary sewer after solids are removed
in a sump. The quench water samples were collected below the bottom ash
hopper because the sump overflow was not accessible.
The quench water grab samples were collected using a 2-1/2 gallon
wide-mouth glass jar. The 2-1/2 gallon jar was filled several times to
obtain sufficient volume for analysis (i.e., 3 times for Unit 4 and 2
times for Unit 3). The contents of the 2-1/2 gallon jar was poured into
clean labeled sample containers (i.e., 4-oz. glass for TOO, 1-L
polyethylene for metals, 1-L glass for organic scan, four 1-L glass for
base/neutral/acid, two 1-L glass for PCS and four 1-L glass for
PCDD/PCDP). The samples were treated with the appropriate preservative
(i.e., sulfuric acid for TOG and organic scan, and nitric acid for
metals), documented on chain-of-custody forms, packed on ice in
Igloo-type coolers, and shipped to the laboratory by priority air
express. The coolers were secured with EPA custody seals.
3-33
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Field leachate - Three field leachate samples were collected during
the follow-up visit to Facility B on October 22, 1986. These field
leachates were grab samples collected from tne northeast corner and the
north and east sides of the landfill. All three of these samples were
collected along the bottom edge of the landfill, where natural leachate
seeps flowed out from underneath the landfill. The seeps then flowed
through a culvert, underneath the road, into a nearby river. The
discharge point of the leachate seeps into the river was observed without
noting any deleterious effects.
The natural seep streams at all three sampling locations were too
shallow to collect a representative sample without disturbing the
sediment. Therefore, the Versar monitoring team used a shovel to dig a
sample collection basin in the leachata scream flow channel. Before the
samples were collected, the leachate stream was allowed to fill the
basin, and the sediment was allowed to settle. After the leachate filled
the basin and was clarified, the samples were collected using a
borosilicate glass beaker and transferred to the appropriate, precleaned
sample containers. -Then, the samples were labeled, documented on
chain-of-custody forms, packed in coolers, iced, and shipped to the
laboratory by priority air express.
3.3.3 Facility C
Versar personnel collected MWC residue samples at Facility C between
September 23, 1986, and September 30, 1986. These samples included:
bottom/fly ash (i.e., a mixture of bottom ash and three discrete fly ash
fractions), fly ash (i.e., a mixture of the three discrete fly ash
fractions), quench water, coarse fly ash (i.e., economizer ash), medium
fly ash (i.e., cooling chamber ash), fine fly ash (i.e., electrostatic
precipitator dust), disposed ash, and ground water (i.e., water from the
facility's production well). Per sampling plan requirements, 25 percent
of these samples were collected in duplicate for quality control (QC)
purposes.
3-34
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The sampling plan for this facility stipulated that Versar personnel
would also collect field leachate and additional ground water samples.
However, the Versar monitoring team was unable to obtain these samples
during this visit. Although evidence of a natural leachate seep was
observed below the landfill, it was dry. Nevertheless, the Versar
monitoring team did observe some surface water runoff (i.e., possibly
field leachate) from the landfill, but the runoff stream was extremely
shallow with a minimal flow volume. Therefore, adequate sample volumes
(approximately three gallons would be required) could not be collected.
Furthermore, because of the extremely shallow depth of the runoff stream,
a representative sample could not be collected without disturbing the
sediment (i.e., disposed ash) over which the runoff was flowing.
The additional groundwater samples were to be collected from three
on-site monitoring wells. However, two of these wells were locked, and
all three wells were equipped with dedicated compressed air pumps (i.e.,
Well Wizards). The Versar monitoring team was unable to gain access to
the keys or the pump operating equipment, and as a result, the wells were
not sampled.
However, at the request of EPA/HWERL, a follow-up visit was scheduled
for October 21, 1986, to obtain the field leachate and monitoring well
samples. Prior to the follow-up visit, Versar contacted the facility's
monitoring well installation and sampling contractor to ensure that the
keys and pumping equipment would be available for sampling. Therefore,
the three ground water samples were collected during this follow-up
visit. Furthermore, because the follow-up visit was scheduled after a
period of heavy rain, Versar was also able to collected three field
leachate samples.
The MWC residue sampling at Facility C commenced during the second
shift (i.e., 3:00 p.m. to 11:00 p.m.) on September 28, 1986, and was
completed at the end of the second shift on September 30, 1986. During
these sampling activities. Unit 1 was down for maintenance; therefore.
3-35
-------
all MWC residue samples were collected from combustion Unit 2. While the
samples were being collected, the incinerator operator recorded pertinent
operating data to be used for evaluating contaminant concentration
differences between shifts and facilities (see Section 5.0).
This operating data is shown in Section 4.1, Table 4.3. Table 3.6 presents
a summary, including field sample numbers, of the samples collected at
this facility. Detailed descriptions of the sampling locations and
procedures for each of the sample matricies are presented below.
Bottom/fly ash - The Versar monitoring team had to collect a
combined ash (i.e., bottom and fly ash mixture) rather than a bottom ash
sample because a discrete bottom ash sampling location was not
available. The bottom/fly ash sample included all the ash types
generated by the facility (i.e., bottom ash, coarse fly ash, medium fly
ash, and fine fly ash). These bottom/fly ash samples were
time-composited samples representing one shift of operation and one
combustion unit (i.e.. Unit 2). Initially, the discrete grab sample
portions of the composite were cpllected each hour over an eight-hour
period, and then manually composited at the end of this period. However,
because of the time required to composite and containerize (including
chain-of-custody documentation, labeling, and preservation) the samples,
the sampling increment was changed to every 40 minutes over a six-hour
period.
Each discrete bottom/fly ash grab sample was collected from the
quench water tank drag conveyor. The drag conveyor exited the quench
water tank and transported the ash up an inclined surface to a load-out
bin, where the ash was discharged into a truck for subsequent disposal.
As the ash was conveyed up the slope, the water returned down the slope
to the quench water tank. However, the ash was still very wet and
contained a large amount of uncombusted material (e.g., glass, cans,
metal scraps, etc.).
The sample increments were collected by stopping the drag conveyor
and taking a stopped-belt cut (ASTM Method D2234-76) across the conveyor
3-36
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TABLE 3.6 SAMPLE IDENTIFICATION CODES FOR FACILITY C
Sample
Matrix
Blank
3 lank-
Description
Field Blank
Trip Blank
Bottom/Fly Composite
Bottom/Fly Composite. Oup
Bottom/Fly Unit 2. 9/28. PM
Bottom/Fly Unit 2. 9/29. PM
Bottom/Fly Unit 2. 9/30. AM
Bottom/Fly Unit 2. 9/30. AM. Oup
Bottom/Fly Unit 2, 9/30. PM
Fly Composite
Fly Unit 2, 9/28, PM
Fly Unit 2. 9/29. PM
Fly Unit 2. 9/29. PM. Oup
Fly Unit 2, 9/30, AM
Fly Unit 2, 9/30, PM
Fly Unit 2. Coarse
Fly Unit 2. Fine (ESP)
Fly Unit 2, Medium
Landfill Perimeter Composite
leachate
Leachate
Leachate
HWell
MWell
MWell
PWell
Quench
Quench
North Side
Northeast Corner
Northwest Corner
#3
M
Production Hell
Unit 2. 9/28
Unit 2. 9/30
TOC
No.
19592
19537
19803
19791
19815
19778
19753
19766
19581
19512
19568
Organic
Scan
No.
19535
19829
19828
19827
19780
19754
19767
19578
19511
19569
Metal j SNA
NO. No.
19536 19525-28
19514
19539
19586
19589
19593
19518
19542
19545
19583
19596
19548
19554
19551
19522
19804 19811-14
19792 19795-98
19816 19823-26
19779 19781-84
197S2 19755-58
19765 19768-71
19582 19570-73*
19513 19501-04*
19557 19558-61
PC8
No.
19533-34
19515
19540
19588
19591
19595
19519
19543
19546
19585
19598
19549
19555
19552
19523
19805-06
19793-94
19817-18
19785-66
19759-60
19772-73
19579-30
19509-10
19566-67
PCDO/
PCDF
No.
19529-32
19516
19541
19587
19590
19594
19520
19544
19547
19584
19597
19550
19556
19553
19524
19807-10
19799-02
19819-22
19787-90*
19761-64*
19774-77*
19574-77*
19505-08
19562-65
Lab
Leachate
No.
19517
19517D
19521
LEGEND:
Bottom/Fly • Combined bottom ash and fly ash samples
Fly - Fly ash
MWell • Groundwater from monitoring well
PWell - Groundwater from production well
Quench - Incinerator quench water
TOC • Total organic carbon
SNA • Base/neutral add ex tractable organ 1cs
• • Samples collected but not analyzed
3-37
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bar using a shovel. The cut was perpendicular to the conveyor direction
and was the width of the shovel. The sides of the cut were as nearly
parallel as possible to prevent particle-size bias. The sample was
placed in a three-gallon container and covered with polyethylene sheeting
to prevent contamination during compositing.
At the end of the compositing period, the material in the bucket was
poured into a polyethylene bag and thoroughly mixed by inverting the bag
several times. Before the sample was containerized, large pieces of
uncombusted material were removed to prevent sample bias. Then, the
homogeneous material was placed into clean sample containers (i.e., one
glass wide-mouth quart jar for each PCDD/PCDP, PCS, and metals sample)
using a small steel garden trowel, and the samples were labeled and
documented on chain-of-custody forms. An additional wide-mouth jar was
filled 1/4 of the way to obtain the bottom/fly ash composite sample for
laboratory leachate testing. This laboratory leachate composite sample
was prepared such that it is representative of the four shifts of
operation during which sampling was performed.
The four bottom/fly ash composite samples and the one bottom/fly ash
laboratory leachate composite were collected during the second shifts on
September 23 and 29, 1986, and the first and second shifts on
September 30, 1986. Additionally, per sampling plan requirements, one of
these samples (i.e., first shift on September 30, 1986) was collected in
duplicate for field and laboratory quality control. The containerized
samples were packed on ice in Igloo-type coolers and shipped to the
laboratory by priority air express.
Fly ash - Similar to the bottom/fly ash samples, the fly ash samples
were time composites representing one shift of operation and one
combustion unit. Also like the bottom/fly ash samples, the fly ash
sampling frequency was changed from every hour for an eight-hour period
to every 40 minutes for a six-hour period. At Facility C, there were
three discrete fly ash fractions that had to be collected individually
3-38
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and than manually composited. These three fractions were the coarse fly
ash, medium fly ash, and fine fly ash.
The coarse fly ash particles settle out of the flue gas stream in
the economizer. The economizer functions by forcing the flue gas through
a series of bends which decrease the stream's velocity. This causes the
larger particles to settle out of the stream because they become too
heavy for the decreased velocity. These settled particles fall down a
chute into a sloped quench water trough, where they are carried to the
quench water tank.
This coarse fly ash fraction was collected at the discharge of the
chute. The sample increments were collected by using a one pint
container to collect a full-stream cut. The full-stream cut was
collected by placing the container underneath the discharge of the chute
and allowing it to fill. The sample was placed in a three-gallon bucket
and covered with polyethylene sheeting to prevent contamination while the
medium fly ash was being collected.
The medium fly ash particles were removed from the flue gas stream
in a cooling chamber. As -the flue gas enters the chamber, cooling water
is sprayed on the gas stream to reduce the temperature and to remove
additional fly ash particles. Then, the cooling water and ash particles
descend through the cooling chamber to a small holding tank at the head
of the quench water trough. Finally, the water and ash particles overflow
the tank and flow down the quench water trough to the quench water tank.
This medium fly ash fraction was collected from the holding tank
before it overflowed into the trough. The sample increments were
collected by thoroughly mixing the contents of the holding tank with a
shovel, and then removing approximately one pint of sample, using the
shovel, and placing the sample in the three-gallon bucket with the coarse
fly ash fraction. Again, the bucket was covered with polyethylene
sheeting while the fine fly ash fraction was being collected.
3-39
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The fine fly ash particles were removed from the flue gas stream in
the final pollution control device, an electrostatic precipitator (ESP).
The ESP comprises a series of parallel metal plates with rigid wires
located between each two plates. The plates are given an electrical
charge (i.e., either positive or negative), while the opposite charge is
imparted to the wires. The charged wires produce coronas which charge
the fine fly ash particles with the opposite charge of the plates. This
causes the particles to adhere to the oppositely charged plates. The
charges alternate between the wires and the plates, subsequently removing
more particles. Each hour, the plates are rapped, and the adhering
particles drop into a collection chamber where they are removed by a
screw conveyor and carried to the quench water tank.
The fine fly ash fraction was collected from a sampling port in this
screw conveyor. The sample increments were collected by removing the
port cover and allowing the port to bleed for approximately one minute.
Then, a one pint sample was collected using a shovel. This sampling
method was analogous to the full-stream cut method used for sampling the
coarse fly ash at the chute discharge. After the sample was obtained, it
was placed in the compositing bucket, and the bucket was covered with
polyethylene sheeting.
At the end of the compositing period, the material in the bucket was
homogenized by pouring the material into a polyethylene bag and mixing.
Then, the homogeneous material was placed into the clean sample
containers, labeled, and documented on chain-of-custody forms. For the
fly ash samples, an additional sample container was filled with 1/2 pint
of the material to obtain a fly ash composite sample for laboratory
leachate testing. Therefore, this sample represented the four shifts of
operation during which sampling was conducted.
The four fly ash composite samples and the fly ash laboratory
leachate samples were collected during the second shifts on September 28,
and 29, 1986, and the first and second shifts on September 30, 1986. Per
3-40
-------
sampling plan requirements, one of these samples (i.e., second shift on
September 23, 1986) was collected in duplicate for field and laboratory
quality control. Three additional grab samples were also collected to
more adequately characterize the fly ash. These were discrete coarse,
medium, and fine fly ash samples which were collected using the
procedures detailed above. These three additional samples were collected
during the second shift on September 29, 1986. The containerized samples
were packed on ice in Igloo-type coolers and shipped to the laboratory by
priority air express.
Quench water - The quench water samples were grab samples collected
in the middle of the shift. This being the case, they were not
representative of the entire shift of operation, but of .only the instant
in time at which they were collected. Therefore, any time-dependent
variability of the quench water contaminant concentrations has not been
accounted for in these samples.
These quench water samples were collected from the end of .a.settling
tank in which the quench water was clarified. As the quench water tank
overflowed, the water and associated debris spilled into this settling
tank. In the settling tank, the debris settled to the bottom, where it
was returned to the quench water tank via a drag conveyor. At the end of
the settling tank, the clarified quench water overflowed a weir into a
sump. The water in the sump is pumped to the local POTW, where it is
treated and discharged.
The quench water grab samples were collected at the overflow weir to
the sump. A stainless steel dipper was used to collect an aliquot of the
overflowing material. The dipper was passed through the overflowing
stream, at a constant speed, and was not allowed to overflow. This
ensured that the grab sample was representative of the entire stream and
was not biased. Next, the water was poured into clean sample containers
(i.e. 1-liter, amber-glass bottles with teflon- lined screw caps), and
the appropriate preservative was added (i.e., nitric acid for metal
3-41
-------
samples and sulfuric acid for total organic carbon and organic scan
samples). Then, the samples were labeled and documented on chain-of-
custody forms. Finally, the samples were placed in Igloo-type coolers
and iced to maintain the chemical and physical integrity of the samples
during transport to the laboratory. These quench water samples were
collected during the second shift on September 28, 1986, and during the
first shift on September 30, 1936.
Production well ground water - During this first sampling visit, the
Versar monitoring team was unable to collect ground water samples from
the facility's monitoring wells. A grab sample was collected from the
facility's production well on September 30, 1986, during the second shift.
This ground water grab sample was collected from a tap at the
facility. First, the tap was fully opened and allowed to discharge for
approximately two minutes to release any trapped sediments or gases.
With the tap still fully opened, the amber-glass sample containers were
filled. Then, the samples were labeled and documented on chain-of-custody
forms, and the appropriate preservative, either nitric or sulfuric acid,
was added. Finally, the samples were packed in a cooler and iced for
shipment to the laboratory.
Landfill perimeter composite (disposed ash) - This sample was
collected on September 29, 1986, to characterize the effects of
weathering on the disposed ash material. The sample was a spatial
composite collected from the perimeter of the landfill and was designed
to adequately represent the wide variety of disposed material. Because
the landfill has been in use since 1970, the individual sample increments
represented a mixture of freshly disposed material as well as older and
more weathered waste residue.
The composite sample was collected using a hand-held auger to obtain
two-foot core sections. The composite comprised 50 of these individual
increments. The distance between sample increments was visually estimated
to yield 50 sampling locations around the landfill's perimeter. Each
3-42
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increment was collected by drilling down two feet, removing the auger
from the hole, and placing the sample core in a compositing bucket.
After the 50 increments were collected, the material in the bucket was
mixed by stirring with a steel garden trowel. Then, the sample was
containerized, labeled, documented, and packed for shipment to the
laboratory.
Blanks - Field blank and trip blank samples were prepared to ensure
that the cleaning water, sample containers, and preservatives were not
sources of sample contamination. The blank samples were high purity
HPLC-grade water poured into the appropriate containers with the required
preservatives added. This HPLC-grade water was used for field cleaning
of sampling equipment. The trip blank samples were prepared at Versar,
and the appropriate preservatives were added to each sample. A trip
blank was prepared for each analyte of interest and was carried to the
facility during sampling activities. The field blank was prepared for
total organic carbon and was prepared while at the facility.
Ground-water monitoring wella - Facility C had three monitoring
wells that were sampled (3, 4, and 17). All three of these wells were
located hydraulically down-gradient of the disposal area between the
landfill and a river. Each monitoring well was equipped with a dedicated
compressed-air pump that was used for evacuation and sampling.
Prior to sampling the ground water, the depth from the top of the
well casing to the water surface was measured and recorded. Then, the
depth from the top of the well casing to the sediment/water interface was
measured and recorded. The difference between these two measurements
yielded the height of standing water in the well. This height was used
to determine the volume of standing water in the well casing and saturated
annulus. A volume of water equal to five times this standing water
volume was pumped from the well to ensure that all water which had been
in prolonged contact with the well casing or the air was removed.
After the well evacuation was completed, a grab sample was obtained
for pH and conductivity analyses. Then, the ground water samples for
3-43
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chemical analysis were collected and placed directly into precleaned
sample containers from the Teflon tubing that was attached to the pump.
Because the water was clear without any visible particulate matter,
filtering of the samples was not required. After being collected, the
samples were labeled, documented on chain-of-custody forms, packed in an
Igloo-type cooler with ice, and shipped to the laboratory by priority air
express.
Field leachate Three field leachate samples were collected during
the follow-up visit to Facility C. These field leachates were grab
samples collected from the north side and the northeast and northwest
corners of the landfill. The northwest corner sample was collected from
an area where a natural leachate seep enters a small stream that flows
underneath the landfill (i.e., through a culvert). The other two samples
(i.e., the north side and the northeast corner) were collected from
surface water runoff streams along the bottom edge of the landfill.
All three field leachate samples were collected using a borosilicate
glass beaker to dip the sample and pour it into the appropriate,
precleaned sample containers. At the northwest corner, sufficient
standing water was available to collect the sample without disturbing the
sediment. However, as previously described in the introduction to this
section, the runoff streams at the north side and northeast corner were
too shallow to collect a representative sample without disturbing the
sediment. Therefore, the Versar monitoring tea.it used a shovel to dig a
sample collection basin in the runoff stream flow channel. Before the
samples were collected, the runoff stream was allowed to fill the basin,
and the sediment was allowed to settle out of the collected leachate.
After the leachate had filled the basin and was allowed to clarify, the
samples were collected by using the borosilicate glass beaker to dip the
sample from the collection basin.
After all the samples were collected and containerized, they were
labeled and documented on chain-of-custody forms. Then, they were packed
in coolers, iced, and shipped to the laboratory by priority air express.
3-44
^;r^\7T™ ;,»^,-;~^77^";j<7!?'~rr?r^Y-""v"iJ^-'r" • <:^"T'-"V' \^''^'^f^^^^^^^^I^}'^'''^^^'J
-------
3.3.4 Facility D
Versar's monitoring personnel collected MWC residue samples, at
Facility D between October 2, 1986, and October 4, 1986. These samples
included: bottom/fly ash (i.e., a mixture of bottom ash and fly ash),
fly ash (i.e., a mixture of economizer ash and electrostatic precipitator
ash), quench water, disposed ash (i.e., a landfill perimeter composite),
and field leachate. Per sampling plan requirements, 25 percent of these
samples were collected in duplicate for quality control purposes. The
Versar monitoring team was unable to collect ground water samples because
Facility D did not have any functional monitoring wells.
The MWC residue sampling at Facility D commenced during the first
shift on October 2, 1986, and was completed at the end of the second
shift on October 4, 1986. During these sampling activities, both Unit
and Unit 2 were operating; however, because of the limited availability
of sampling locations, the individual units could not be sampled
separately. Therefore, the MWC residue samples were representative of
both units operating in combination. While the' samples were being
collected, the incinerator operator recorded pertinent operating data to
be used for evaluating contaminant concentration differences between
shifts and facilities (see Section 5.0). This operating data is
presented in Section 4.1, Table 4.4. Table 3.7 presents a summary,
including field sample numbers, of the samples collected at Facility D.
Detailed descriptions of the sampling locations and procedures for each
of the sample matricies are presented below.
Bottom/fly ash - The Versar monitoring team had to collect a
combined ash (i.e., bottom and fly ash mixture) sample at Facility D
because a discrete bottom ash sampling location was not available. The
bottom/fly ash sample included all the ash types generated by the
facility (i.e., bottom ash, economizer ash, and electrostatic
precipitator ash). These bottom/fly ash samples were time composites
representing one shift of operation and the average of both combustion
3-45
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TABLE 3.7 SAMPLE IDENTIFICATION COOES FOR FACILITY 0
Sample
Matrix
Blank
3 lank
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Sample
Description
Field Blank
Trip Blank
Composite
Unit 1-2. 10/3. AM
Unit 1-2. 10/3. PM
Unit 1-2. 10/4, AM
Bottom/Fly Unit 1-2. 10/4. AM. Oup
Bottom/Fly Unit 1-2. 10/4. PM
Fly Composite
Fly Composite, Oup
Fly Unit 1-2. 10/3. AM
Fly Unit 1-2, 10/3, AM, Oup
Fly Unit 1-2, 10/3, PM
Fly Unit 1-2. 10/4. AM
-Fly Unit 1-2, 10/4, PM
Landfill Perimeter Composite
Leachate • Northeast Corner
Leachate Northeast Corner, Oup
Leacnate Southeast Corner
TOC
No.
19713
19725
Organic PCOO/
Scan Metals SNA PCS PCOF
No. No. No. No. NO.
19722 19726 19714-17 19724-25 19718-21
19639
19627
19614
19625
19612
19675
19682
19688
19691
19709
19667
19670
19679
19635
19706
19599
19638 19628-31
19626 19615-18
19613 19602-05
19677
19684
19690
19693
19712
19600
19636-37
19623-24
19610-11
Lab
Leachate
No.
19678
19676
19683
19689
19692*
19711
19669
19672
19681
19687
19708
19668
19671
19680
19686
19707
19673
19674
19601
19632-35
19619-22
19606-09
Quench Unit 2, 10/3 19651 19648
Quench Unit 2, 10/3, Oup 19664
Quench Unit 2. 10/4 19704 19702
19652 19640-43
19665 19653-56
1970S 19694-97
19649-50
19662-63
19703.27
19644-47
19657-60
19698-01
LEGEND:
Bottoa/Fly - Conblned bottom ash and fly ash samples
Fly - Fly ash
MWell • GroundlMter from monitoring well
Quench « Incinerator quench water
TOC - Total organic carbon
SNA • Base/neutral acid axtractable organics
• • Sample collected but not analyzed
3-46
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units (i.e.. Unit 1 and Unit 2). The discrete grab sample increments
used to prepare the composite were collected every 40 minutes for a
six-hour period.
At Facility D, bottom and fly ash were discharged into and collected
in two quench water tanks, one for each combustion unit. After being
quenched, the ash material was subsequently discharged onto a belt
conveyor and transported to a load-out hopper, where it was loaded into a
truck for haulage to the landfill. Due to the nature of the operation,
the belt conveyor could not be stopped to collect unit-specific bottom/
fly ash samples. Therefore, the samples had to be collected at the load-
out hopper where the ash from each unit was mixed.
The sample increments were collected as the load-out hopper
discharged into the truck. A shovel was used to collect a full-stream
cut (ASTM Method 02234-76) of the ash material as it fell into the
truck. The shovel was moved through the falling material at a uniform
rate to collect a representative portion of the falling stream. This
sample portion was placed in a three-gallon bucket, which was covered
with polyethylene sheeting to prevent contamination during the
compositing period.
At the end of the compositing period, the material in the bucket was
poured into a polyethylene bag and thoroughly mixed by inverting the bag
several times. Before the sample was containerized, large pieces of
uncombusted material were removed to prevent sample bias. Then, the
homogeneous material was placed into clean sample containers (i.e., one
glass wide-mouth quart jar for each PCDD/PCDF, PCB, and metals sample)
using a small steel garden trowel, and the samples were labelled and
documented on chain-of-custody forms. An additional wide-mouth jar was
filled 1/4 of the way to obtain the bottom/fly ash composite sample for
laboratory leachate testing. This laboratory leachate composite sample
was prepared in such a way that it was representative of the four shifts
of operation during which sampling was performed.
3-47
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Th« four bottom/fly ash composite samples and the one bottom/fly ash
laboratory leachata composite were collected during the first and second
shifts on October 3 and 4, 1986. Additionally, per sampling plan require-
ments, one of these samples (i.e., first shift on October 4, 1986) was
collected in duplicate for field and laboratory quality control. The
containerized samples were placed in Igloo-type coolers with ice and
carried to the laboratory by the Versar monitoring team.
Fly ash - Similar to the bottom/fly ash samples, the fly ash samples
were time composites representing one shift of operation and the average
of the two combustion units. Also like the bottom/fly ash samples, the
fly ash samples were collected every 40 minutes over a six-hour period.
However, unlike the bottom/fly ash samples, the fly ash sample increments
had to be collected from each combustion unit individually. Consequently,
because the operating capacities of the units were similar, equal volumes
of fly ash were collected from each unit and manually composited.
Facility D generated two different fly ash fractions—coarse fly ash
and fine fly ash. The coarse fly ash fraction is removed from the flue
gas stream in an economizer. The economizer is simply a series of bends
that decrease the flue gas velocity causing the coarse particles to
settle out of the stream and fall down a chute to the quench water tank.
The fine fly ash fraction is removed from the flue gas by a series of
electrically charged parallel plates in the electrostatic precipitator
(ESP). The fine ash particles have a static charge which causes them to
be attracted to the oppositely charged plates. The charges on the plates
are alternately changed from positive to negative, subsequently removing
more of the oppositely charged particles. Each hour, the plates are
rapped, and the adhering fine ash particles fall into a screw conveyor
which carries the material to the chute where it joins the economizer
ash. The fly ash sample increments were collected from sampling ports in
this chute.
The sample increments were collected by using a stainless steel
dipper to obtain a full-stream cut of the falling material. The sampling
3-48
-------
port cover was removed, and the dipper was inserted perpendicular to the
falling stream. Because the dipper opening cross-sectional area was
approximately equal to the interior cross- sectional area of the chute,
it was ideal for collecting a representative unbiased cut. The dipper
was held in the part and allowed to fill without overflowing. Then, the
sample increment was placed in a compositing bucket, and the bucket was
covered with polyethylene sheeting. This procedure was repeated for each
unit collecting equal sample portions (i.e., one full dipper) from each.
At the end of the compositing period, the material in the bucket was
homogenized by pouring the material into a polyethylene bag and mixing.
Then, the homogeneous material was placed into precleaned sample
containers, which were labeled and documented on chain-of-custody forms.
Two additional 1-quart sample containers were partially filled with
1/2 pint of each shift composite fly ash to obtain duplicate fly ash
composite samples, for laboratory leachate testing. Therefore, these two
samples represented the four shifts of operation during which sampling
was conducted. .
The four fly ash composite samples.and the two fly ash laboratory
leachate samples were collected during the first and seconds shifts on
October 3 and 4, 1986. Per sampling plan requirements, one of these
samples (i.e., first shift on October 3, 1986) was collected in duplicate
for field and laboratory quality control. The containerized samples wers
placed in Igloo-type coolers with and carried to the laboratory by the
Versar monitoring team.
Quench water - The quench water samples were grab samples collected
in the middle of the first shifts on October 3 and 4, 1986. Consequently,
they were not representative of the entire shift of operation, but of
only the instant in time at which they were collected. Therefore, any
time-dependent variability of the quench water contaminant concentrations
has not been accounted for by these samples.
3-49
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The quench water samples were collected from the end of the quench
water tank using a stainless steel dipper. Unlike the bottom/fly and fly
ash samples that were representative of both combustion units, the quench
water samples were representative of only Unit 2 because an adequate
(based on safety considerations) sampling location was not available for
Unit 1. The samples were collected by placing the dipper in the quench
water tank and allowing it to fill. Then, the collected sample was
split equally among the required number of pracleaned sample containers
(i.e., eleven 1-liter amber-glass bottlas and one 4-ounce TOC bottle per
sample). On October 3, 1986, a duplicate sample was collected by
splitting each dipper among two complete sets of glass containers. The
reason for splitting each filled dipper among the required containers was
to prevent sample bias arising from each discrete grab. This procedure
was repeated until all of the sample .bottles were full.
After the sampling was completed, the appropriate preservative (i.e.,
nitric acid for metal samples and sulfuric acid for total organic carbon
and. organic scan samples) was added to each sample, and the containers
were securely capped. Then, the samples were labeled and documented on
chain-of-custody forms. Finally, the samples were placed in Igloo-type
coolers and iced to maintain the physical and chemical integrity of the
samples during transport to the laboratory.
Landfill perimeter composite (disposed ash) - This sample was
collected October 2, 1986, to characterize the effects of weathering on
the disposed ash material. The sample was a spatial composite collected
from the perimeter of the landfill designed to adequately represent the
wide variety of disposed material. Because the landfill has been in
continuous use for several years, the individual sample increments
represented a mixture of freshly disposed material as well as older and
more weathered waste residue
The composite sample was collected using a hand-held auger to obtain
two-foot core sections. The composite comprised 50 of these individual
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sections. The distance between sample increments was visually estimated
to yield 50 sampling locations around the landfill's perimeter. Each
increment was collected by drilling down two feet into the material,
removing the auger from the hole, and placing the sample core in a
compositing bucket. After the 50 increments were collected, the material
was mixed by vigorously stirring with a steel garden trowel. Then, the
sample was containerized, labeled, documented, and packed on ice for
shipment to the laboratory.
Field leachate - Three field leachate samples were collected at
Facility 0 on October 2, 1986. Facility 0 has a leachate collection
system installed for the landfill, however, the system was obstructed, so
no leachate could be obtained. Leachate samples were collected from
natural depressions where surface water runoff and natural seeps
collected along the bottom of the landfill. The field leachates were
grab samples collected from two of these depressions at the southeast and
northeast corners of the landfill. The sample from the northeast corner
was collected in duplicate for quality control purposes.
All three field leachate samples were collected using a stainless
steel dipper. The dipper was placed in the depression and allowed to
fill with leachate. Then, the sample increment was split equally among
the required number of precleaned sample containers (i.e., eleven 1-liter
amber-glass bottles and one 4-ounce TOG bottle for the southeast corner,
and twice as many containers for the duplicate samples at the northeast
corner) to prevent sampling bias. This procedure was repeated until all
of the samples bottles were full. The sample containers were securely
capped, labeled, and documented on chain-of-custody forms. Finally, the
samples were placed in coolers, iced, and personally delivered to
Versar's laboratory by the field team.
Blanks - Field and trip blanks were prepared to ensure that the
cleaning water, sample containers, and preservatives were not sources of
sample contamination. The blank samples were high purity HPLC-grade
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water/ which was used for field cleaning of sampling equipment, poured
into the sample containers with the appropriate preservatives added. The
trip blanks were prepared at Versar and were carried to the facility
during sampling activities. The field blank was prepared for total
organic carbon, while at the facility.
3.4 Sample Preparation and Analysis Procedures
The solid residue samples (e.g., fly ash, bottom ash, and disposed
ash) and the liquid samples (e.g., field leachate, ground water, and
quench water) that were collected from the specified facilities using the
procedures detailed in Sections 3.3.1 through 3.3.4 were analyzed to
determine the concentrations of various toxic metals and organic
compounds. The solid samples were prepared for metal analyses using
SW-846 Method 3050 (i.e., acid digestion) and for PCB analysis using
modified SW-846 Method 3540 (i.e., soxhlet extraction) with a 1:1 mixture
of hexane and acetone as the extraction solvent. The solid samples for
PCDD/PCDF analyses were prepared according to the protocols specified in
the analytical method (see Appendix B). For analytical QA purposes,
25 percent of the samples were collected in duplicate and submitted to
the laboratory as "blind" field duplicates. Blanks, laboratory
duplicates, spiked samples, and check standards were analyzed according
to specification in the procedure and at a minimum frequency of 5 percent.
In addition to these solid and liquid samples, leachates were
prepared in the laboratory from the solid residue samples and analyzed
for metals and organics. The laboratory leachates were prepared from
composites of the solid samples (i.e., one fly ash and one bottom ash
composite per facility) by using three different extraction techniques:
Extraction Procedure (EP), Toxicity Characteristics Leaching Procedure
(TCLP), and Mono-filled Waste Extraction Procedure (MWEP; SW-924). These
leaching procedures and the analytical methods are described in the
following sections.
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3.4.1 Laboratory Leachates
The laboratory leachate composite samples from each facility were
subjected to three different leaching procedures in attempt to compare
the data resulting from the use of three commonly accepted extraction
methods. These leaching procedures were developed in order to
standardize the extraction procedure used and to approximate natural
leaching potential in the absence of field leachate composition data by
determining the type and quantity of leachable chemical constituents
within a solid waste. The leaching characteristics of the wastes are
essential input data for designing landfills and leachate treatment
facilities. Additionally, the EP and TCLP methods have regulatory
significance; the leaching characteristics from these methods are used to
classify a solid waste as hazardous or non-hazardous under the Resource
Conservation and Recovery Act (RCRA). Conversely, the MWEP method was
developed only to provide leaching characteristic information and has no
regulatory significance. A summary of the conditions for these leaching
procedures is provided in Table 3.3. A brief description of each
leaching procedure is presented below.
Extraction Procedure (EP) - This laboratory leaching procedure was
applied to composite samples of fly ash and bottom (or bottom/fly) ash
from each facility. Since this procedure was developed to classify a
solid waste as hazardous or non-hazardous based on predetermined hazard
levels for 14 specific constituents, the analytical results from these
EP-prepared residues may be used to formulate regulatory strategies and
to evaluate the adequacy of current disposal practices. Therefore, the
EP test procedure was followed very closely. Assuming the collected
solid residue sample contained no filterable liquid (i.e., it contained
only surface and interstitial moisture), the EP method was performed as
follows:
1. Obtain a representative 100-gram sample of residue.
2. Crush material to <9.5 mm, if necessary.
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Table 3.3. Suamry Conditions for EP, TO.P, and HHEP Methods
Conditions
Liquid.-Solid Ratio
Extraction Medium
pH Control
Extraction Tim
Agitation Method
Temperature Control
Particle Size
Hunter of Extractions
EP (1)
20:1
0.5N acetic acid
5
24 hours
Tuabler
20-40 C
< 9.5 itn
1
Tap (2)
20:1
0.1N acetate buffer
5
18 hours
Tunbler 9 28-32 rpa
19-25 C
< 9.5 im
1
MNEP (3)
10:1 per extraction
Distil led/delonlzed water
None
18 hours per extraction
Tunbler
24-26 C
< 9.5 ma
4. sequentially (4)
(1) EP - Extraction Procedure (40 CFR 261. Appendix II).
(2) TCLP - Toxldty Characteristic Leaching Procedure (Revised 40 CFR 261. Appendix II).
(3) MMEP - Motion lied Haste Extraction Procedure (A Procedure for Estimating Monofllled Solid
waste Leachate Composition, Technical Resource Document SW-924, 2nd Edition).
(4) For this project, a modified MHCP method was used with two sequential extractions
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3. Place sized solid residua in extractor vassal.
4. Add amount of daionized water equal to 16 times the weight of
the solid residue.
5. Begin agitation and measure pH.
5a. If pH >5.0. adjust to 5.0 ± 0.2 with 0.5N acetic acid.
5b. If pH <5.0, no adjustment is necessary.
6. Continue monitoring pH at specified intervals adjusting pH as
required in 5a for 6 hours.
7. Agitate mixture for a total of 24 hours between 20-40°C.
7a. If at the end of 24 hours the pH > 5.2, adjust to 5.0 ±
0.2 and continue agitation for an additional 4 hours.
7b. If pH <5.2, no additional agitation is necessary.
8. Add required amount of daionized water and filter mixture using
a 0.45 m membrane filter.
9. Analyze or preserve filtrate (i.e., laboratory leachate) as
required.
If the residue sample contained filterable liquid, the sample was
first separated into its component phases (i.e., the sample was
filtered), and the above procedure was carried out on the solid phase.
Then, the initial filtrate and extract from the solid phase were combined
for analysis. Finally, the EP leachate was analyzed for metals, total
organics (i.e., organic scan), and if the IOC results from the MWEP
extract exceeded 5 mg/L, organic constituents (i.e., BNA's). As
specified in the sampling plan, 25 percent of these samples were
collected, prepared, and analyzed in duplicate as blind (i.e., to the
analysts) QA/QC samples.
Toxicity Characteristic Leaching Procedure (TCLP) - Like the EP
method, this laboratory leaching procedure was applied to composite
samples of fly ash and bottom (or bottom/fly) ash from each facility.
The TCLP method was developed to replace EP as the hazardous waste
classification criteria under RCRA. The TCLP classification criteria are
based on all Appendix VIII (40 CFR 261) constituents, including volatiles,
while EP classifications are based on predetermined hazard levels for only
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14 spacific contaminants. Therefore, the analytical results from the
TCLP-prepared extracts nay be more likely to be applied to a broader
range of waste types than those from the EP-prepared extracts. Assuming
that the solid residue sample contained no filterable liquid, the TCLP
method was performed as follows:
1. Obtain a representative 100-gram sample of residue.
2. Crush material to <9.5 mm, if necessary, and place residue in
extraction vessel.
3. Determine appropriate extraction medium:
3a. Weigh out 5-gram subsample of residue; reduce particle size
to <1 mm, if required; place sample in a 500 ml beaker.
3b. Add 96.5 ml of distilled/deionized water (ASTM Type II).
3c. Stir sample vigorously for 5 minutes with magnetic stirrer.
3d. Measure pH, and if pH <5 use Extraction Fluid 1.
3e. If pH >5, add 3.5 ml iTON HC1; slurry for 30 seconds; heat
to 50°C for 10 minutes.
3f. Allow mixture to cool to room temperature and measure pH.
3g. If pH <5, use Extraction Fluid 1, and if pH >5, use
Extraction Fluid 2.
4. Add amount of extraction fluid selected in Step 3 equal to
20 times the weight of the solid residue.
5. Close extraction vessel, and agitate in rotary extractor device
at 30 •»• 2 rpm for 13 hours, maintaining the temperature at
22 ± 3"C.
6. Filter material through a 0.6 to 0.3 urn glass fiber filter.
7. Analyze or preserve filtrate as required.
If the residue sample contained filterable liquid, the sample was
first separated into its component phases, and the above procedure was
carried out on the solid phase. Then, if the initial filtrate and solid
extract were compatible (i.e., did not form multiple phases or precipi-
tates upon combination), they were combined together for analysis. If
these liquids were incompatible, they were analyzed separately, and the
results were mathematically combined to yield the total leachable
composition of the solid residue sample. Finally, the TCLP leachate was
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analyzed for metals, total organic3 (i.e., organic scan), and BNA's (i.e.,
if the IOC results from the MWEP extract exceeded 5 mg/L). Although not
specified in the scope of work, the TCLP leachates were also analyzed for
PCOO/PCDF at the request of EPA/OSW to determine whether this method
would extract these hazardous organic compounds. As specified in the
contract, 25 percent of these samples were collected, prepared, and
analyzed in duplicate as blind QA/QC samples.
Mono-filled Waste Extraction Procedure (MWEP) - As was the case for
the EP and TCLP methods, this laboratory leaching procedure was applied
to composite samples of fly ash and bottom (or bottom/fly) ash from each
facility. The MWEP method was developed to estimate the quantity of
potentially leachable constituents in a given solid waste and to measure
the concentration of these constituents in extracts produced by various
solid to liquid extraction ratios. This procedure includes a sequential
four-step batch extraction which produces data that can be used to
construct an aqueous extraction profile for each of the constituents.
For this MWC residue study, however, Versar used a modified MWEP method
with only two sequential batch extractions. Unlike the EP and TCLP
methods, the MWEP has no regulatory significance. The justification for
using this method is its applicability to mono-filled wastes only, which
was one of the facility selection criteria (See Section 3.1.1). The
modified MWEP method was performed as follows:
1. Obtain subsample and determine percent solids.
2. Obtain representative sample equal to 100 grams dry weight and
place in extraction vessel.
3. Add appropriate amount of distilled/deionized water to give a
10:1 liquid to solid weight ratio, taking into account the
moisture determined in step one.
4. Extract (i.e., agitate using a tumbler) the mixture for 13 hours
at a temperature of 25 ± 1°C.
5. Filter mixture through a 0.45 urn nitrocelluse membrane filter
(for inorganic analyses) or a 0.6 - 0.3 urn glass fiber filter
(for organic analyses).
3-57
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6. Retain filtrate for subsequent analysis. Place in properly
cleaned sample container and preserve as required.
7. Place filter cake (i.e., solid residue) back into extraction
vessel and add 1 liter of fresh distilled/deionized water.
3. Repeat steps 4 through 6.
9. Analyze the two sequential extracts separately.
Each of the two extracts ware analyzed for metals, total organics
(i.e., organic scan), and total organic carbon (TOG). If the TOG
concentration of either extract was greater than 5 mg/L, then the EP and
TCLP extracts, as well as both MWEP extracts, were analyzed for organic
constituents (i.e., BNA's). The EP and TCLP extracts were not analyzed
for total organic carbon because an organic acid (i.e., acetic acid) was
used for pH control during the leaching procedure. As specified in the
sampling plan, 25 percent of these samples were collected, prepared, and
analyzed in duplicate as blind QA/QC samples to determine the
reproducibility of sampling, preparation, and analysis procedures,
3.4.2 Analyses
Analyses required by the Scope of Work included total organic
carbon, total metals (i.e., As, Cd, Cr, Cu, Pe, Hg, Mn, Ni, Pb, Se, and
Zn), organic scan, PCQD/PCDF, and PCB's. Additionally, the analysis of
organic constituents (i.e., BNA's) was required contingent upon the
results of the total organic carbon and organic scan analyses. All of
these analyses were conducted using EPA-approved procedures. Table 3.9
provides the analytical methods, techniques, and detection limits for
these analyses. It should be noted that although Table 3.9 gives the
primary analytical method reference (e.g., SW-346 and MCAWW), the methods
were applied as modified by the Contract Laboratory Program (CLP)
Statement of Work for the applicable analytes (i.e., metals and BNA's).
A brief description of the analytical methods used for each parameter is
presented below.
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Table 3.9. Sunery of Analytical Methods and Detection Halts
Liquid Samples (1)
Solid Samples (2)
Parameter
Total Organic Carbon
Organic Scan
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Zinc
PCOO/PCOF's
PCB's
Organic Constituents
Analytical
Method (3)
MCAWW-415.1
MCAMM18.1
MCAWM-206.2
MCAWW-200.7
MCAWW-200.7
MCAWW-200.7
MCAWN-200.7
MCAWW-239.2
MCAWM.200.7
MCAWW-245.1
MCAWM.200.7
MCAWH-270.2
MCAHW-200.7
Appendix B
Appendix C
ORG-625
Analytical
Technique (4)
COMB/OXIO
IR SPEC
Furnace AA
I CAP
I CAP
I CAP
I CAP
Furnace AA
I CAP
Cold Vapor AA
I CAP
Furnace AA
I CAP
HRGC/HRMS
HRGC/EIMS
6C/MS
Detection
Limit (5)
1 rag/L
0.25 ng/L
10 ug/L
5 ug/L
10 ug/L
25 ug/L
100 ug/L
5 ug/L
15 ug/L
0.2 ug/L
40 ug/L
5 ug/L
20 ug/L
20 ng/L
S-50 ug/L (6)
10-50 ug/L (7)
Analytical
Method (3)
N/A
N/A
SH846-7060
SW846-6010
SW846-6010
SW846-6010
SW846-M10
SW846-7421
SH846-6010
SW846-7471
SW846-6010
SW846-7740
SW846-6010
Appendix B
Appendix C
N/A
Analytical
Technique (4)
N/A
N/A
Furnace AA
I CAP
I CAP
I CAP
I CAP
Furnace AA
I CAP
Cold Vapor AA
I CAP
Furnace AA
I CAP
HRGC/HRMS
HRGC/EIMS
N/A
Detection
Limit (5)
N/A
N/A
1.0 mg/kg
0.5 rag/kg
1.0 mg/kg
2.5 ng/kg
10 mg/kg
0.5 ng/kg
1.5 mg/kg
0.02 mg/kg
4.0 mg/kg
0.5 ng/kg
2.0 mg/kg
20 ug/kg
0.2-1 ug/kg (6)
N/A
N/A - Not Applicable; these analyses will not be conducted on solid samples.
(1) - Liquid samples include: field leachate. quench water, ground water, and laboratory leachate.
(2) - Solid samples include: fly ash, bottom ash, disposed ash, etc. Solid samples will be prepared for metals analyse?
using SW-846 Method 3050—Acid Digestion.
(3) - Referenced analytical methods are fro* the primary sources listed below, however, these methods will be applied
as modified by Contract Laboratory Program (CLP) Statement of Work for metals and organic constituents.
MCAHW - U.S. EPA, Methods for Chemical Analysis of Water and Wastes. March 1983 (EPA-600/4-79-020).
ORG - U.S. EPA, Methods for Organic Chemical Analysis of Municipal and Industrial Wastewater. July 1982 (EPA-600/4-.a
SW846 • U.S. EPA, Test Methods for Evaluating Solid Wastes - SW-846, April 1984.
Appendix B • Analytical Procedures to Assay Stack Effluent Samples and Residual Combustion Products for
Polychlorinated 01benzo-p<0toxins (PCDO) and Polycnlorinated Olbenzofurans (PCOF). Group C - Environmental
Standards workshop (ASME. U.S. DOE. and U.S. EPA), September 1984.
Appendix C - Method 680. Determination of Pesticides and PCBs in Water and Soil/Sediment by Gas Chromatography/Msss
Spectrometry, U.S. EPA, EMSL. Cincinnati. OH, November 1985.
(4) - COMB/OXIO - Combustion/Oxidation; IR SPEC - Infrared SpectrophotometHc; I CAP - Inductively Coupled Argon
Plasma; HRGC/HRMS - High Resolution Gas Chronatography (Capillary Column)/H1gh Resolution Mass Spectrometry
HRGC/EIMS - High Resolution Gas Chrometography/Electron Impact Mass Spectrometry; GC/MS - Gas Chromatography/
Mass Spectrometry.
(5) - Detection limits are Contract Required Detection Limits (CRDLs) from CLP for metals and organic constituents.
(6) - Detection limits increase with increasing level of chlorlnatlon. Solid samples will be prepared for PCB analyses
using SW-846 Method 3540—Soxhlet Extraction.
(7) . Detection limits for individual constituents are listed 1n the iwthod.
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Total Organic Carbon (TOC) - Total organic carbon analysis was
performed on all field water samples (i.e., field leachate, quench water,
and ground water) and laboratory leachate prepared using MWEP. The
results of the total organic carbon analyses were used to initiate the
BNA contingency analysis. Each field water sample that had a TOC con-
centration of greater than 5 mg/L was analyzed for BNA's. Additionally,
if either of the two MWEP extracts contained greater than 5 mg/L TOC,
then the EP, TCLP, and both MWEP extracts were analyzed for BNA's.
The TOC analysis was performed by converting the organic carbon in
the sample to carbon dioxide by catalytic combustion. Then, the carbon
dioxide was measured using infrared detection. Prior to analyzing each
batch of samples, the infrared detector was calibrated by analyzing a
blank and three standards, and plotting a curve of peak area (from a
strip chart recorder) versus concentration. Finally, the measured amount
of carbon dioxide in the sample (i.e., the peak area) was compared to the
calibration curve to determine the TOC concentration of the sample.
Organic Scan - The organic scan was performed on all field water
samples and laboratory leachates to determine whether organic compounds
other than PCDD's, PCDF's, and PCB's were present. The organic scan was
performed by acidifying the sample to pH <2 and extracting it with
fluorocarbon 113 in a separatory funnel. The extract was analyzed using
an infrared spectrophotometer that was calibrated before each batch of
samples using five calibration standards that bracketed the expected
sample concentration. The calibration curve was constructed by plotting
the absorbence of these standards versus their respective concentrations,
and the organic content of the sample was determined by direct comparison
of its absorbence to the standards.
Metals - Total metal analyses were performed on all field water
samples, laboratory leachates, and solid samples. The solid samples and
liquid samples containing particulate matter were prepared using EPA
Method 3050 (SW-846), as modified by CLP, which is an acid digestion
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procedure. After the sample was digested, it was analyzed using the
appropriate technique: Cold Vapor Atomic Absorption (Hg), Graphite
Furnace Atomic Absorption (As, Pb, and Se), or Inductively Coupled Argon
Plasma (Cd. Cr, Cu, Fe, Mn, Mi, and Zn).
The Cold Vapor AA technique is a flameless AA procedure based on the
absorption of radiation by mercury vapor. First, the mercury was reduced
to the elemental state and aerated from solution in a closed system.
Then, the mercury vapor passed through a cell positioned in the light
path of an AA spectrophotometer. The spectrophotometer was calibrated
before each day of analysis using a blank and five mercury standards to
construct a calibration curve of absorbence versus micrograms of mercury.
The absorbence of the sample (i.e., peak height on a strip-chart recorder)
was compared to the calibration curve to determine the mercury concentra-
tion of the sample.
The Graphite Furnace technique also used an AA spectrophotometer to
determine the metal concentration. The spectrophotometer was calibrated
daily before analysis for each metal by using a blank and three calibra-
tion standards that bracketed the expected sample concentration. The
standards were analyzed, and internal curves of absorbence versus
concentration were constructed by a microcomputer. This calibration
procedure had to be performed each time a new metal was analyzed.
For Graphite Furnace AA analysis, a representative aliquot of the
sample was placed in a graphite tube within the furnace, evaporated to
dryness, charred, and atomized. Concurrently, energy (i.e., a beam of
light at a wavelength specific to the metal of interest from a hollow
cathode tube) was directed through the graphite tube containing excited
energy level atoms of the vaporized metal. The intensity of the trans-
mitted radiation was used to determine the absorbence (A = 2 - log % T),
which is directly proportional to the concentration of the metal atoms
contained in the vapor. This absorbence was measured, and the specific
metal concentration was determined by direct comparison to standards
(i.e., the internal calibration curve).
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Unlike the previous two methods, the ICAP procedure can be used to
measure the concentrations of several different metals, concurrently..
The previous two methods can only quantify one particular metal in each
sample aliquot, but they were used because they generally offer greater
sensitivity (i.e., a lower detection limit).
Prior to analysis each day, the ICAP instrumentation was calibrated
for each metal analyte of interest by using two blanks (i.e., calibration
blank and a reagent blank) and three standards that bracketed the
anticipated sample concentrations. Before analyzing these standards, the
analyst entered the actual standard concentrations for each metal into
the ICAP computer. Subsequently, during the analysis of the calibration
standards, the computer generated initial calibration curves based on
these entered concentrations and the characteristic atomic-line spectra
intensities.
During ICAP analysis, the sample was reduced to a fine spray (i.e.,
an aerosol) and transported to a plasma torch where excitation occurred.
Then, characteristic atomic-line spectra were produced for each metal
present in the aspirated sample, and these spectra were dispersed by a
grating spectrometer. Finally, the intensities of the dispersed metal
characteristic spectral lines were compared to standards (i.e., the
internal calibration curves) to yield the concentration of each metal in
the sample.
PCDD/PCDF - PCDD/PCDF analyses were performed on all fly ash
samples. When the results of these analyses showed concentrations of
total PCDD's or PCDF's in any of the four fly ash samples from a given
facility exceeding 5 ng/g, the bottom (or bottom/fly) ash samples,
TCLP-prepared leachates, field leachate samples, and quench water samples
from that facility were analyzed for PCDD/PCDF. The analytical method is
designed to quantify the individual homologs (homolog refers to the total
number of chlorine atoms in the organic structure, but not to the
position of those atoms) in the tetra- through octa-chlorinated classes/
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but not to quantify the individual isomers within these classes. One
notable exception was the 2,3,7,3-TCDD isomer, which was quantified. The
PCDO/PCDF analyses were performed by Versar's subcontractor. Battalia
Columbus Laboratories. The analytical method used by Battalia is
included in this report as Appendix B.
The first step of this analytical method was a sample extraction
procedure using the appropriate organic solvent(s). Next, the extract
was subjected to a sequence of liquid chromatography elutions to remove
co-extracted interferences. Then, the cleaned extract was introduced
into a capillary column gas chromatography instrument with a high
resolution mass spectrophotometer for identification and quantification
of the individual constituents. Prior to analyzing for PCDD/PCDF, the
GC/MS system was calibrated using three standards that bracketed the
expected sample concentration range. Finally, the homologs were
identified and quantified by comparison of their retention times and mass
spectral intensity ratios to those of the calibration standards.
PCB's - Analysis of PCB's was performed on all fly ash samples. If
the results of the PCDD/PCDF analyses triggered the analysis of bottom
(or bottom/fly) ash samples, field leachates, and quench water samples
from a given facility as discussed above, the contingency analyses for
PCB's were also performed on these samples. Similar to the PCDD/PCDF
analytical method, the PCB method was used to identify and quantify the
PCS homologs, and not the individual isomers.
All field water samples were analyzed by EPA Method 630 subtitled
"Determination of Pesticides and PCBs in Water and Soil/Sediment by Gas
Chromatography/Mass Spectrometry." The analytical method is incorporated
into this report as Appendix C.
This method was recommended by Ms. Ann Alford-Stevens of EPA Environ-
mental Monitoring and Support Laboratory (EMSL) in Cincinnati, Ohio.
Method 630 is a published, validated method for water samples only. It
is the most current GC/MS analytical procedure for the determination of
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PCBs identified and measured as isomer groups or horoologs. Also
developed with the method is a software package which automates the data
reduction to the full-scan GC/MS data generated by the method.
EPA Method 680 does not provide a procedure for extraction of PCBs
from solid samples, however. The Versar laboratory tested and adapted
SW-346 Method 3540, a general extraction procedure, to the extraction of
PCBs from fly ash and combined bottom/fly ash samples. Preliminary tests
were conducted using the 20 fly ash samples from the four facilities to
verify that the extraction procedure was valid. These tests and the
results are described below.
• Method Tests
The method tests consisted of two trial runs of the method using a
blank, a standard, and a real ash sample. The combined methods to be
tested included the following steps:
1. Soxhlet extraction of the fly ash with acetone/hexane
2. Acid cleanup of the extract
3. Micro florisil column cleanup of the extract
4. Full scan GC/MS analysis of the samples
5. Data reduction using the automated software for Method 680
For the first test, the test "samples" were processed through all of
the steps listed above. The results indicated a serious problem with the
method. No surrogates were recovered. The problem was determined to be
in the extraction process. Overall there did not seem to be any major
problems with applying the analytical procedures to the samples, but the
problem with surrogate recovery had to be resolved.
A second test was initiated. For the second test, the cleanup
procedures, which were suspected to be the problem, were omitted. The
surrogates were recovered. The analysis showed that the second test was
an improvement over the first but that there were still some problems.
Additional tests showed that there were losses occurring during the
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concentration step of the final extract. After rinsing the walls of the
concentration vessel, the recoveries were much better.
After the second test is was decided to proceed with samples without
the cleanup. The cleanup was suspected of contributing to the recovery
deficiency/ and the samples analyzed did not present an analytical
problem without the cleanup.
• Fly Ash Extraction Method 3540 Summary
Samples were extracted using SW-846 Method 3540 adapted to ash
samples. Twenty grams of the ash samples were weighed out. Each sample
aliquot was spiked with stable labeled PCS surrogates (carbon
4-chlorobiphenyl, carbon 3,3'-4,4'-tetrachlorobiphenyl, carbon
2,2',3,3',5,5',6,6'-octachlorobiphenyl, and carbon decachloro-
biphenyl). Soxhlet extraction with 1:1 acetone/hexane was performed for
16 hours.
The extract was then concentrated to a final volume of 50 ul for
analysis. The following changes were made to the method: sample size
was increased to 20 grams, no sodium sulfate was added to the sample
during extraction, and the final volume was adjusted to 50 ul.
• Fly Ash Analysis Method 680 Summary
Samples were analyzed using U.S. EPA Method 630. Four surrogates
were added to samples prior to extraction, and one internal standard was
added to each extract before GC/MS analysis. The analysis was performed
on a Finnigan 5100 GC/MS DS. The chromatographic column used was a Restek
RTX-5 30-meter 0.32 mra-id fused silica capillary column temperature
programmed from 80C to 302C at 15C per minute. Samples were injected in
the splitless mode. The scan range was 45-550 amu.
Prior to analysis, the system was calibrated to FC-43 and adjusted
to meet U.S. EPA calibration requirements for 10 ng of DFTPP. An initial
five point calibration curve was generated by injecting 1 ul aliguots of
calibration standards supplied by EMSL Cincinnati. The calibration curve
3-65
-------
was checked daily with a continuing calibration check standard before
each 12-hour sequence..
PCBs were identified and measured by isoraer group (homolog). The
automated software utilizes characteristic mass spectral features of PCBs
at each level of chlorination for identification. Additional mass spectral
confirmation checks were made by chemists after the automatic selection
and quantification of PCBs was completed. Adjustments to the PCS
concentration were made in those instances where additional professional
mass spectral interpretation disagreed with the confirmation made by the
automated data reduction program. The additional checks consisted of
verifying acceptable quantitation and confirmation ion ratios, presence of
M-70 confirmation ion, and absence of M+70 and M+35 interfering ions.
• Detection Limits
Method 630 does not provide PCS isomer method detection limits or a
method for the determination of detection limits. Due to the nature of
the analysis, a rigorous method may not be possible. However, in order
to better understand the meaning of the data and illustrate its
limitations, estimated detection limits were derived. They are stated in
the method to be in a working range of 1 ng to 10 ng. Based on this
information, and the information obtained from preliminary method
evaluation, Versar's best estimates for detection limits of the PCS
homologs are listed below.
Estimated Detection Limits for the PCS Homologs
Using Method 630 for Fly Ash Analysis
Isomer Group ug/kg
Monochlorobiphenyls 0.2
Dichlorobiphenyls 0.3
Trichlorobiphenyls 0.4
Pentachlorobiphenyls 0.6
Hexachlorobiphenyls 0.6
Heptachlorobiphenyls 0.7
Octachlorobiphenyls 0.3
Nonachlorobiphenyls 0.9
Decachlorobiphenyl 1.0
3-66
-------
The fly ash samples were extracted in two separate groups consisting
of samples from Facilities A and B, and from Facilities C and D,
respectively. Extraction of the first group was begun on November 13,
and completed on November 17, 1986. The remaining ash samples were
extracted November 18 through November 20.
Sodium- sulfate was initially omitted from the extraction process.
No problems were observed during the method development from this
modification. The extracts from the first group of samples (extracted
November 13) resulted in the formation of two layers upon concentrating.
In some instances, these layers could both be organic resulting in
partitioning of the analyte. In addition, distinct layers in the extract
could be a result of water. Sodium sulfate was, therefore, incorporated
into all further extractions. An equal weight of sodium sulfate was added
to the soxhlet extractor; in addition, the extract was poured through a
sodium sulfate column into the Kudema-Danish (KD) flask.
The low surrogate recoveries of the carbon 13 monochlorobiphenyl and
tretrchlorobiphenyl for the extractions dated November 13 were a result
of the final concentration step. The extract was transferred from the
ampule to a 1 ml conical vial. The ampule was rinsed with 10 1 ml
aliquots. Each rinse aliquot was blown down with nitrogen gas in a 1 ml
conical vial. This probably resulted in the loss of lighter molecular
weight (higher vapor pressure) congeners. As a result, a 5-ml conical
vial was used instead of the 1 ml vial. In addition, an emphasis was
placed on passing a gentle stream of nitrogen over the extract.
Precipitation of crystals during the concentration step presented a
potential problem with the absorption of the analyte to the crystalline
particulates. To alleviate this problem, the extract was passed through
a micro sodium sulfate column during the concentration. The columns were
rinsed thoroughly with hexane to minimize the loss of the analyte.
Incorporating the modifications discussed, the technique used in all
extractions after November 13 was as follows. The extract was
3-67
-------
concentrated to approximately 10 ml in a KD flask. The extract and
rinsings were passed through a pipette containing sodium sulfate into a
50 ml centrifuge tube. The extract was gently blown to 3 ml. If the
precipitation of particulates occurrad again, an additional filtering was
performed. The extract was then transferred to a 5 ml conical vial and
gently concentrated to 50 ul. During concentration, the sides of the
vial were rinsed thoroughly. Once concentrated to 50 ul, the vial was
centrifuged to ensure the viscous extract collected exclusively at the
bottom of the conical vial.
Organic Constituents (BNA's) - The analysis for BNA's was performed
on field water samples (i.e., quench water, ground water, and field
leachates) and laboratory leachates contingent upon the results of the
TOC and organic scan analyses. If the TOG and/or organic scan results
exceeded 5 rog/L for any of these samples, then, the sample was also
analyzed for BNA's.
Prior to initiating calibration or analysis, the standard mass
spectral abundance criteria were established for the GC/MS system. This
was accomplished by analyzing a 50 ng injection of decafluorotriphenyl-
phosphene (DFTPP) and tuning the system as necessary. The criteria were
demonstrated daily or for each twelve-hour period of operation, whichever
was more frequent. After the tuning criteria were established by using
DFTPP, but prior to initiating sample analysis, the GC/MS system was
initially calibrated using five standards that contained all the required
compounds.
The organic constituents were determined by extracting the samples
with methylene chloride using a continuous extractor, and analyzing the
extract using gas chronatography/mass spectrometry (GC/MS). The
individual organic constituents were identified and quantified using
retention times and extracted ion current profiles.
3-63
-------
4.0 RESULTS AND DISCUSSION
After the laboratory analyses were completed as detailed in
Section 3.4, the analytical results were summarized by sample matrix,
analytical parameter, and facility. These summaries include: the
facility operating parameters during sampling; the analytical results of
each sample, including blanks; averages and standard deviations of each
analytical parameter by sample matrix and facility; and QC data,
including relative percent differences (RPDs) for each set of "blind"
field duplicate and laboratory duplicate samples and recoveries for
spiked samples. These summary tables were evaluated to determine any
significant trends in the data between facilities, sample types (i.e.,
matrices ), shifts, and combustion units. The summary tables and
evaluations are presented in the following sections.
4.1 Facility Operating Parameters
During the sampling activities at each facility, the incinerator
operator recorded hourly operating parameters. These operating
parameters were collected to determine whether differences in the
parameters significantly affect tha MWC residue composition. The
operating data were used in an attempt to explain significant differences
between shifts of operation, combustion units, and/or facilities (see
Section 5.3). Tables 4.1, 4.2, 4.3, and 4.4 provide the operating
parameters for Facilities A, B, C, and D, respectively.
These tables include the unit, date, shift, time, feed rate, ram
speed (related to feed rate), probe temperature, steam production rate,
combustion air, and electrostatic precipitator (ESP) specifications. The
unit refers to the combustion unit number from which the samples were
collected, while the date and shift refer to the date and shift of
operation during which the samples were collected. The time indicates
when the operating parameters were recorded. The next parameter on the
table, feed rate, is expressed as both buckets and tons. The buckets
indicate the number of feed crane loads that were fed into the charging
4-1
-------
TABLE 4.1 SUMMARY OF FACILITY A OPERATING PARAMETERS
Feed Rate Ran Speed
Unit Date
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
1 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
2 9/26
Shift
AM
AM
AM
AM
AM
AM
AM
AM
PM
PM
PM
PM
PM
PM
PM
PM
AM
AM
AM
AM
AM
AM
AM
AM
PM
PM
PM
PM
PM
PM
PM
PM
Tim (Buckets)
700
300
900
1000
1100
1200
1300
1400
TOTAL
AVERAGE
1500
1600
1700
1800
1900
2000
2100
2200
TOTAL
AVERAGE
700
300
900
1000
1100
1200
1300
1400
TOTAL
AVERAGE
1500
1600
1700
1800
1900
2000
2100
2200
TOTAL
AVERAGE
5
4
5
5
5
6
5
5
40
NA
6
5
5
4
4
3
4
0
31
NA
4
5
4
3
4
3
4
4
31
NA
4
4
5
3
5
4
6
0
31
NA
(tons)
3.5
2.8
3.5
3.5
3.5
4.2
3.5
3.5
28
NA
4.2
3.5
3.5
2.8
2.8
2.1
2.3
0
21.7
NA
2.3
3.5
2.8
2.1
2.3
2.1
2.3
2.8
21.7
NA
2.8
2.8
3.5
2.1
3.5
2.3
4.2
0
21.7
NA
(Units)
40
40
30
45
50
35
30
50
NA
40
20
0
0
30
30
20
40
NA
20
10
15
15
10
15
10
20
5
NA
12.5
20
10
15
30
10
20
NA
17.5
Probe
Temp.
Corijustlon Air
Steam Total Overflre
(F) (ib/hr) (Units) (Units)
1,000
980
1,100
1.000
1,320
1.060
1.380
1,020
NA
1.333
920
300
410
850
750
1,110
940
NA
826
1,100
1.C80
1.080
1,200
1,060
1,340
1.040
1.200
NA
1,100
1,120
1,300
1,000
1.020
1,350
1.080
1.110
NA
1,097
26,000
23,000
32.000
28,300
30.000
32.000
30,300
28.000
229.300
28,625
28,000
15,000
5.000
27,000
20.000
29,000
25.000
149,000
21,286
24,300
26,300
23,000
26.000
23.300
23.000
22,000
28.000
195.000
24.375
28,000
35,300
26,000
22.000
28,300
24.300
27,000
190,000
27.143
50
50
65
65
65
65
65
65
NA
61
70
0
0
70
70
70
70
NA
50
28
28
28
28
28
28
28
28
NA
28
30
28
30
30
32
32
30
NA
30
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
40
40
40
40
40
40
40
40
NA
40
0
0
HA
0
ESP (Outlet)
(Kv)
24
24
26
24
26
26
26
28
NA
26
22
23
22
22
25
26
23
NA
23
28
24
30
28
28
30
28
NA
28
25
28
28
29
24
28
30
NA
27
(«*)
160
160
200
120
120
240
240
320
NA
195
130
110
110
130
140
140
100
NA
123
400
300
440
450
260
460
240
NA
364
250
420
380
220
220
220
350
NA
294
4-2
-------
TABLE 4.2 SUMMARY OF FACILITY 3 OPERATING PARAMETERS
Feed Rat* Ram Speed
Unit Date Shift
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
9/28
9/28
9/28
9/28
9/29
9/29
9/29
9/29
9/28
9/28
9/28
9/28
9/29
9/29
9/29
9/29
AM
AM
AM
AM
PM
PM
PM
PM
AM
AM
AM
AM
PM
PM
PM
PM
Tim (Buckets) (tons)
300
1000
1200
1400
TOTAL
AVERAGE
1600
1800
2000
2200
TOTAL
AVERAGE
800
1000
1200
1400
TOTAL
AVERAGE
1600
1800
2000
2200
TOTAL
AVERAGE
19
19
19
19
76
NA
19
19
19
19
76
NA
21
21
21
21
34
NA
20
20
20
20
80
NA
13.3
13.3
13.3
13.3
S3. 2
NA
13.3
13.3
13.3
13.3
53.2
NA
14.7
14.7
14.7
14.7
58.8
NA
14
14
14
14
56
NA
(Units)
34
34
35
35
NA
34.5
25
28
34
33
NA
30
24
22
19
NA
21.7
19
22
23
27
NA
22.75
Probe
(F)
1,650
1,450
1,500
1,350
NA
1,488
1.425
1,300
1,250
1,400
NA
1,344
1,250
1,303
1,345
1,422
NA
1,330
1,373
1,369
1,241
1.251
NA
1,309
Stean
Corimstlon Air ESP
Total Overf 1re Zone #1 Zone »2
(Ib/hr) (Units) (Units)
30,000
30,000
80,000
30.000
320.000
30.000
30.000
80.000
76,000
84,000
320,000
80,000
99,000
100,000
99,000
100,000
398,000
99.500
105,000
109,000
105,000
94,000
413.000
103,250
45
30
45
45
NA
41
20
55
100
50
NA
56
42
NA
42
69
70
84
85
NA
77
27
27
24
23
NA
25
20
26
19
19
NA
21
22
22
22
22
NA
22
18
18
18
18
NA
18
(nA)
39
39
39
89
NA
39
89
89
89
89
NA
89
56
48
48
88
NA
60
24
28
24
16
NA
23
(oft)
107
107
107
107
NA
107
107
107
107
107
NA
107
104
104
104
92
NA
101
60
44
40
35
NA
45
4-3
-------
hopper during the previous hour. The tons were then calculated from the
bucket number by using the approximate feed crane capacity. The ram
speed is also a relative measure of the feed rate, however, it is a
relative measure of the feed rate into the incinerator, rather than into
the charging hopper. The charging ram (see Figure 3.1} forces the
material from the charging hopper into the combustion chamber. The probe
temperature indicates the temperature in the incinerator, but because we
are not aware of the exact probe location, it is a relative temperature
and should not be directly compared between facilities. The next
parameter, steam production rate, indicates the pounds per hour of steam
generated at the three energy recovery facilities. The combustion air is
a relative measure of the amount of air needed in excess of the
stoichiometric requirement for complete combustion. The combustion air
can be either overfire, which is forced into the combustion chamber from
above the combustion zone, or underfire, which is forced into the
combustion chamber through the grates below the combustion zone.
Finally, the ESP specifications are relative measures of-the power
consumption by the ESP, As the level of fly ash particulates in the flue
gas increase, the ESP power consumption must increase to maintain an
adequate removal efficiency.
4.2 Solid Samples
The solid samples collected included: fly ash, combined bottom/fly
ash, bottom ash, and landfill perimeter composite (i.e., disposed ash).
Each of these samples were analyzed for metals, PCBs, and PCDO/PCDFs, and
the results were summarized and evaluated. Sections 4.2.1 through 4.2.3
present the analytical result tables for each parameter summarized by
sample matrix and facility and a narrative evaluation of these results.
4.2.1 Metals
The solid samples were analyzed for total cadmium (Cd), chromium
(Cr), copper (Cu), iron (Fe), lead (Pb), manganese (Mn), nickel (Ni),
4-6
-------
zinc (Zn), arsenic (As), selenium
-------
TABLE 4.5 TOTAL METALS DATA FOR SOLID SAMPLES
FLY ASH
Facility
A
A
A
A
A
B
a
a
a
a
c .
c
c
c
c
0
Sample
Description
Unit 1. 9/26. AM
Unit 1. 9/26. AM. Oup
Unit 1, 9/26, PM
Unit 2, 9/26. AM
Unit 2. 9/26. PM
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 3, 9/28, AM
Unit 3. 9/28. AM, Oup
Unit 3, 9/29. PM
Unit 4, 9/28, AM
Unit 4, 9/29, PM
FACILITY B AVERAGE
STANDARD DEVIATION
Unit 2. 9/28. PM
Unit 2, 9/29. PM
Unit 2. 9/29. PM. Oup
Unit 2. 9/30. AM
Unit 2. 9/30, PM
FACILITY C AVERAGE
STANDARD DEVIATION
Unit 1-2. 10/3. AM
0 Unit 1-2, 10/3, AM, Oup
0
0
0
Unit 1-2, 10/3, PM
Unit 1-2, 10/4, AM
Unit 1-2, 10/4, PM
FACILITY 0 AVERAGE
STANDARD DEVIATION
Cd
mg/kg
193
186
215
222
138
190.3
29.6
322
316
251
381
475
349.0
75.3
107
191
157
223
188
173.2
39.1
259
172
286
210
206
226.6
40.6
Cr
ng/kg
79
66
57
66
76
70.8
5.6
105
98
74
97
100
94.3
10.3
76
54
52
48
49
55.3
10.3
77
67
93
89
90
83.2
9.8
Cu
mg/kg
2380
2040
1870
1250
1040
1716
499
745
724
588
912
854
765
112
1050
531
556
484
485
621
216
516
518
597
486
510
525
38
F«
ng/kg
17400
15000
9730
20200
15900
15646
3444
9900
9350
5960
16200
22300
12742
5812
9030
8200
8450
16700
14400
11356
3511
3320
7190
3790
8960
9170
8486
706
Pb
rag/kg
5550
5400
5660
5480
5090
5636
243
7350
7270
5280
9230
14400
3706
3109
3260
3490
3130
3420
2830
3226
234
5450
4600
5770
4740
4430
4998
519
Mn
mg/kg
1010
1020
1060
807
1090
997
99
895
389
824
1310
1070
998
176
320
388
382
341
353
357
25
857
751
1250
1410
1190
1092
248
N1
mg/kg
106
91
98
97
160
110
25
80
76
52
67
68
69
.10
130
102
95
245
212
157
61
63
55
36
89
36
76
14
Zn
mg/kg
15700
14500
15100
17400
9480
14436
2660
32700
31800
23600
34000
38800
32180
4923
10200
10300
8460
10600
9940
9900
750
22100
18600
23900
17600
17300
19900
2630
As
mg/kg
41.9
38.0
48.8
36.3
16.0
36.3
11.0
106
39.9
79.0
131
149
111.0
25.3
29.0
16.2
17.7
26.3
32.2
24.4
6.3
50.7
54.5
60.4
47.2
43.2
51.2
5.9
Se
mg/kg
<5
<5
<5
<5
<5
2.5
0
<10
<10
10.0
11.7
15.6
9.5
4.1
4.9
7.6
6.2
7.6
3.3
7.0
1.3
9.6
9.1
15.5
10.7
9.6
10.9
2.4
Hg
mg/kg
27
23
35
25
24
26.3
4.3
9.3
8.0
12
19
21
13.9
-5.2
1.3
5
4.0
3.1
1.4
3.0
1.5
1.3
2.0
1,4
0.94
l.Q
1.4
9.4
TOTAL NUMBER 20 20
MINIMUM 107 48
MAXIMUM 475 105
OVERALL AVERAGE 235 76.2
STANDARD DEVIATION 85 17.2
20 20 20 20 20 20 20 20
484 5960 2830 320 52 3460 16 2.5
2380 22300 14400 1410 245 38800 149 15.6
907 12058 5642 861 103 19104 55.7 7.5
550 4611 2534 335 49 8901 36.4 4.0
4-8
-------
TABLE 4.5 TOTAL METALS DATA FOR SOLID SAMPLES
COMBINED BOTTOM AND FLY ASH
Facility
A
A
A
A
A
C
C
C
C
C
0
0
0
Sample •
Description
Unit I. 9/26. AM
Unit 1, 9/26, PM
Unit 2. 9/26, AM
Unit 2. 9/26. AM. Dup
Unit 2. 9/26, PM
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 2, 9/28, PM
Unit 2, 9/29, PM
Unit 2. 9/30, AM
Unit 2. 9/30, AM, Oup
Unit 2. 9/30, PM
FACILITY C AVERAGE
STANDARD DEVIATION
Unit 1-2, 10/3. AM
Unit 1-2, 10/3, PM
Unit 1-2, 10/4, AM
0 Unit 1-2. 10/4. AM. Dup
0
Unit 1-2. 10/4, PM
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
Cd
ng/kg
17
13
17
IS
37
19.8
8.7
7.8
10
24
27
20
17.8
7.6
45
18
17
18
23
24.2
10.6
IS
7.8
45
20.6
9.5
Cr
ng/kg
25
19
12
16
12
16.8
4.9
22
332
19
26
37
87.2
122.6
38
28
31
36
43
35.2
5.3
15
12
332
46.4
76.9
Cu
ng/kg
452
387
369
377
193
356
86
329
5900
3420
608
5900
3231
2432
424
1060
289
728
524
505
269
15
193
5900
1397
1921
Fe
ng/kg
5130
6500
6650
9140
2100
5904
2300
5220
22300
5040
9720
16000
11656
6650
24500
3000
8590
95100
19000
31038
32638
15
2100
95100
16199
22073
Pb
mg/kg
633
585
2200
1140
1670
1246
619
259
6950
1700
1060
13200
4634
4884
3410
819
571
612
688
1220
1098
15
259
13200
2366
3324
Mn
ng/kg
281
331
134
251
188
247
56
110
339
155
1810
254
534
643
462
797
3130
640
544
1115
1014
15
110
3130
632
782
N1
ng/kg
21
30
22
24
13
22.0
5.5
44
556
42
38
93
154.6
201.7
37
25
26
119
82
57.8
37.0
15
13
556
78.1
131.0
In
ng/kg
1810
1480
1730
3050
1980
2010
544
545
1520
1570
3250
2980
1973
1005
2950
1920
2400
46000
2390
11132
17437
15
545
46000
5038
10971
As
ng/kg
6.1
2.9
7.9
12.2
4.7
6.8
3.2
4
4.7
5.7
7
22.8
3.8
.7-l
16.4
4.3
5.4
6.1
6.4
7.7
4.4
15
2.9
22.8
7.77
5.21
Se
ng/kg
<0.5
<2.S
<5
<5
<0.5
1.4
1.0
1.4
<5.
<5.
<0.5
<5.
1.8
0.9
<2.5
<1
<1
«l
<2.5
0.3
0.4
15
0.25
2.5
1.327
0.910
Hg
ng/kg
S.8
3.9
6.9
5.0
3.7
6.3
1.7
0.51
0.21
0.62
0.13
0.59
0.4
0.2
0.12
0.16
0.21
0.13
0.11
0.1
0.0
IS
0.11
8,7
2.276
2.980
4-9
-------
TABLE 4.5 TOTAL METALS DATA FOR SOLID SAMPLES
BOTTOM ASH
Facility
8
3
3
B
3
Facility
Sample
Description
Unit 3, 9/28. AM
Unit 3. 9/29, PM
Unit 4. 9/28. AM
Unit 4, 9/28, AM, Oup
Unit 4. 9/29. PM
No.
M1n.
Max.
Avg.
Std. Oev.
Sample
Description
Cd
mg/kg
2.3
1.1
3.8
3.5
43
5
1.1
43
10.74
16.16
Cd
mg/kg
Cr
mg/kg
105
24
66
78
33
5
24
105
61.20
29.67
Cr
mg/kg
Cu
mg/kg
10700
7250
792
581
1720
5
581
10700
4209
4060
Cu
mg/kg
Fe
mg/kg
12000
27100
115000
24100
17500
5
12000
115000
39140
38290
LANDFILL
Fe
mg/kg
Pb
mg/kg
2920
1380
2140
3930
3630
5
1380
3930
2800
942
Mn
mg/kg
1520
430
1010
938
538
5
430
1520
887
387
N1
mg/kg
35
17
36
90
29
5
17
90
41.4
25.2
Zn
mg/kg
1930
914
2350
5760
12400
5
914
12400
4671
4194
As Se
mg/kg mg/kg
3.4 <5.
2.2 <5.
8.9 <5.
6.9 <5.
24.6 <5.
5 5
2.2 2.5
24.6 2.5
9.20 2.50
8.06 0.00
Hg
mg/kg
0.36
0.13
0.12
0.12
0.13
S
0.12
0.36
0.17
0.09
COMPOSITE
Pb
mg/kg
Mn
mg/kg
N1
mg/kg
Zn
mg/kg
As Se"
mg/kg mg/kg
Hg
mg/kf
C Perimeter Composite 8.7
0 Perimeter Composite 30
85 1190 60600 709 572 120 4740 6.0 <5 0.5)
52 402 19600 1210 455 51 2050 14.3 <2.5 0.1$
4-10
-------
although the metal concentrations were typically lower in the weathered
ash than in freshly generated ash, considerable metal concentrations
remain in the weathered ash suggesting that a major portion of the metals
in the ash may not be readily mobile to the environment.
Upon comparing the concentrations of metals in the fly ash to those
in the combined bottom/fly and bottom ash, some interesting observations
arose. First, the variability between shifts, units, and facilities was
substantially higher for the combined and bottom ash than it was for the
fly ash. In fact, the variability between shifts and units for the
bottom/fly and bottom ash was greater than the variability between
facilities for the fly ash. This observation was expected because of the
heterogeneous nature of the bottom/fly and bottom ash based on the
diverse range of particle sizes compared to the more homogeneous nature
of the fly ash. This heterogeneity made it extremely difficult to
collect representative, comparable samples, as evidenced by the standard
deviations. Second, the concentrations of cadmium, mercury, chromium,
lead, nickel, zinc, selenium, and arsenic were between 1.5 and ten times
higher in the fly ash than in the bottom/fly or bottom ash. Third, the
concentrations of copper and iron are approximately two times higher in
the bottom/fly and bottom ash than they are in the fly ash. Finally, the
concentration of manganese is approximately equivalent for both ash
fractions.
4.2.2 Polychlorinated Biphenyls (PCBs)
The solid samples were analyzed for individual PCB homologs and
total PCBs. The results of these analyses are tabulated and summarized
in Table 4.6.
A review of the PCB homolog concentrations in the fly ash showed
that the variability between shifts and units was relatively small, while
the variability between facilities was relatively large. Facility D had
the highest concentration of total PCBs, as well as the highest
concentration of each individual PCB homolog,.followed by Facility B,
4-11
-------
TABLE 4.6 PCBs IN SOLID SAMPLES
FLY ASH
Plant
A
A
A
A
A
3
a
a
a
a
c
c
c
c
c
c
c
c
0
0
0
0
0
Sanple
Description
Unit 1, 9/26, AM
Unit 1. 9/26, AM, Oup
Unit 1. 9/26. PM
Unit 2, 9/26, AM
Unit 2. 9/26. PM
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 3, 9/28, AM
Unit 3. 9/28, AM, Oup
Unit 3. 9/29, PM
Unit 4, 9/28, AM
Unit 4. 9/29, PM
FACILITY B AVERAGE
STANDARD DEVIATION
Unit 2. 9/28. PM
Unit 2. 9/29, PM
Unit 2, 9/29. PM. Oup
Unit 2. 9/30, AM
Unit 2. 9/30, PM
Unit 2, Coarst
Unit 2. Fine (ESP)
Unit 2, Hedlun
FACILITY C AVERAGE
STANDARD DEVIATION
Unit 1-2. 10/3, AM
Unit 1-2, 10/3, AM, Oup
Unit 1-2. 10/3. PM
Unit 1-2, 10/4, AM
Unit 1-2, 10/4, PM
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
MONO
-CB
ng/g
0.64
0.64
0.00
0.5
0.29
0.40
0.10
0.38
1.46
0.47
0.94
0.41
6
0.29
1.46
0.707
0.382
01
-CB
ng/g
0.7
0.73
1.37
0.13
0.73
0.44
2.01
0.38
1.19
0.32
0.31
0.49
0.65
0.16
2.88
2.42
5
7.37
1.34
4.00
2.21
13
0.13
7.87
2.048
2.111
4-12
TRI
-CB
ng/g
0.52
0.52
0.00
2.32
1.34
2.43
2.20
0.53
2.91
1.72
5.27
7.67
1.98
3.91
2.26
9
0.52
7.57
2.962
2.079
TETRA PENTA
-C8 -CB
ng/g ng/g
2.72 0.87
2.5
2.45
2.56. 0.37
0.12 0.00
2.41
1.02
2.16
5.52 2.25
1.31
2.48 2.25
1.60 0.00
8 2
1.02 0.87
5.52 2.25
2.511 1.560
1.270 0.690
TOTAL
PCS
ng/g
0.7
0.73
1.89
0.77
0
0.32
0.61
0
0
8.92
3.34
5.55
3.66
3.41
0
0
0.31
0
0.49
0
0
0
0.16
0.29
8.2
5.16
13.31
24.77
5.6
11.41
7.28
20
0
24.77
4.037
6.005
-------
TABLE 4.6 PC3S IN SOLID SAMPLES
COMBINED BOTTOM AND FLY ASH
Plant
A
A
A
A
A
C
C
C
C
C
0
0
0
0
0
MONO
Saople -CB
Description ng/g
Unit 1. 9/20, AM
Unit 1. 9/26, PM
Unit 2. 9/26. AM
Unit 2, 9/26, AM, Oup
Unit 2. 9/26, PM
NUMBER OF PCBs FOUND 0
Unit 2, 9/28, PM
Unit 2. 9/29, PM
Unit 2. 9/30, AH
Unit 2, 9/30, AM, Oup
Unit 2, 9/30, PM
NUMBER OF PCBs FOUND 0
Unit 1-2. 10/3. AM
Unit 1-2. 10/3, PM
Unit 1-2, 10/4, AM
Unit 1-2, 10/4, AM, Oup
Unit 1-2. 10/4. PM
NUMBER OF PCBs FOUND 0
TOTAL NUMBER 0
MINIMUM NA
MAXIMUM NA
OVERALL AVERAGE NA
STANOARO DEVIATION NA
01
-CB
ng/fl
0.66
1
0
1.35
0.126
2
3
0.126
1.35
0.71
0.50
TRI
-CB
ng/g
0
0
0.35
5.66
2.79
14.3
9.52
5
5
0.35
14.3
6.52
4.94
TETRA PENTA TOTAL
-CB -CB PCS
ng/g ng/g ng/g
0
0.66
0
0
0
0 0 1
0
0
0
0
0
000
0.35
5.66
2.79
16.5. 32.15
9.646
1 0 3
1 0 15
16.5 NA 0
16.5 NA 32.15
16.50 NA 3.42
0.00 NA 8.13
4-13
-------
TABLE 4.6 PCBs IN SOLID SAMPLES
BOTTOM ASH
MONO 01 TRI TETRA PEHTA TOTAL
Sample -CB -CB -C8 -CB -CB PCS
Plant Description ng/g ng/g ng/g ng/g ng/g ng/g
B Unit 3. 9/28. AN 0
8 Unit 3. 9/29, PH ' 0
3 Unit 4. 9/28, AN 0
3 Unit 4. 9/28, AN. Oup 0
3 Unit 4. 9/29. PM 0
NUMBER OF PCBs FOUND 030000
LANDFILL COMPOSITE
MONO 01 TRI TETRA PENTA TOTAL
Sample 'CB -C9 -CB -CB -CB PCS
Plant Description ng/g ng/g ng/g ng/g ng/g ng/g
C Perimeter Composite 41.5 225 109 375.5
0 Perimeter Composite 0.689 2.36 1.54 4.589
4-14
-------
Facility A, and Facility C, which had the lowest concentration of each
PCS homolog. The di-, tri-, and tetra-CB horoologs were the moat
prevalent and were of approximately equal magnitude, while the mono- and
Penta-CB homologs were also approximately equal, but substantially less
prevalent than the di-, tri-, and tetra-CB homologs. The higher
chlorinated PCS homologs (i.e., the PCB homologs more highly chlorinated
than the Penta-CB class) were not detected in any fly ash sample.
A review of the PCB data in Table 4.6 for the combined bottom/fly ash
and bottom ash (Facility B) showed that only Facility 0 had measurable
concentrations of PCBs in each sample. Therefore, the variability between
facilities was significantly high. Only one sample from Facility A
(Unit 1, 9/26, PM) had a detectable, although minimal, PCB concentration
of 0.66 ng/g. Facilities B and C did not have any samples in which PCBs
were detected. As was the case for the fly ash, the di-, tri-, and
tetra-CB homologs were the most prevalent. In fact, these were the only
PCB homologs detected in any of the combined ash samples. The tri-CB
homolog was detected in all five samples from Facility D, while the
tetra-CB homolog was detected in only one sample from Facility 0. The
di-CB homolog was detected in two samples from Facility 0 and in one
sample from Facility A.
The landfill perimeter composite samples also contained only the
di-, tri-, and tetra-CB homologs. The PCB concentration of the landfill
composite from Facility 0 was approximately equal to the PCB concentration
in the combined ash samples from Facility D, as expected. However, the
PCB concentration for the landfill composite from Facility C was the
highest found in any sample (375.5 ng/g), yet the combined ash samples
from this facility did not contain any detectable PCBs. It was
anticipated that the results from Facility C would have exhibited the
same trend noted for Facility D; however, several different contributing
factors may have caused this seemingly erroneous result from Facility C.
First, an organic interference (see discussion of analytical procedures
in Section 3.4.2) in the landfill composite sample may have caused an
4-15
-------
erroneously high PCS result for this sample. Second, because of the
heterogeneous nature of the disposed ash, some "pockets" of concentrated
ash may have been sampled and subsequently biased the composite. Third,
an outside source of PCBs may have contaminated the ash once the residue
had been placed in the disposal area. One potential outside source of
PCBs was the bulldozer or other diesel powered equipment used at the
landfill. Typically, this equipment uses hydraulic fluids that may
contain PCBs. If these hydraulic fluids were leaking, they may have
contributed to the high concentration of PCBs in the landfill perimeter
composite, especially since the bulldozer operates principally around the
landfill's perimeter.
Upon comparing the PCS concentrations of the fly ash with those of
the combined and bottom ash, the following observations were noted.
First, the variability between shifts, units, and facilities for the
combined/bottom ash was substantially higher (i.e., where measurable
quantities were detected) than for the fly ash. This is due to the
heterogeneity of the combined/bottom ash compared to the homogeneity of
the fly ash. Second, the PCS concentrations of the fly ash were
significantly higher than those for the combined/bottom ash. This
indicates that the PCBs may condense on the fine fly ash particles or
physically adhere to them and are negligible in the coarse bottom ash
material. Third, only the di-, tri-, and tetra-CB homologs were detected
in both the fly ash and combined ash, and the mono- and penta-CB homologs
were found only in the fly ash. This indicates that the bottom ash alone
is not a source of mono- or penta-CB homologs, and it dilutes the
concentration of these homologs below detectability in the combined ash.
This observation is supported by the bottom ash data for Facility B.
Finally, Facility D had the highest concentrations of PCBs for both the
fly ash and combined ash, and Facility C had the lowest PCB concentrations
for both ash fractions.
4-16
-------
4.2.3 Polychlorinated Dibenzo-p-dioxins and Polychlorinated
Dibenzo-furans (PCDD/PCDFs)
The solid samples were analyzed for individual PCDD and PCDF
homologs in the tetra- through octa-chlorinated classes. Additionally,
the 2,3,7,8-TCDD and 2,3,7,8-TCDF isomers were identified and quantified.
The results of these analyses are tabulated and summarized by sample
matrix and facility in Table 4.7.
A review of the PCDD homolog concentrations in the fly ash showed
that the variability of the homolog concentrations between units and
shifts was relatively small, and the variability of these concentrations
between facilities was extremely large. Facility C had the highest
concentration of total PCDOs, as well as the highest concentration of each
PCDD homolog. Additionally, Facility C had the highest concentration of
the 2,3,7,8-TCDD isomer. After Facility C, Facility B had the second
highest concentration of each PCDD homolog, followed by Facility 0 and
Facility A, which had the lowest concentration of each PCDD homolog. The
hexa-CDD homolog was the most prevalent at three of the four facilities
(it was the third most prevalent at Facility B), and the tetra-CDD
homolog was the least prevalent at all four facilities. Approximately
5 percent of the total tetra-CDDs was the 2,3,7,8-TCDD isomer. Finally,
one significant trend was noted, as the total PCDDs increased, the hexa-
through octa-chlorinated classes abundance increased disproportionately
(i.e., when the total PCDD concentration was less than 500 ng/g, the
hexa- through octa-chlorinated classes accounted for 70 percent of the
total PCDD concentration, however, when the total PCDD concentrations
exceeded 500 ng/g, the hexa- through octa-chlorinated classes accounted
for 90 percent of the total PCDD concentration).
At Facility C, two discrete fly ash fractions were also analyzed for
PCDDs. The first of these, the coarse fly ash (i.e., economizer ash),
did not contain any detectable PCDDs. However, the second of these
fractions, the fine fly ash (i.e., electrostatic precipitator ash),
contained the highest PCDD concentrations of any fly ash sample that was
4-17
-------
TABLE 4.7 ?CDO AND PCOF IN SOLID SAMPLES
FLY ASH (OIOXIN HOMOLOGS)
Plant
A
A
A
A
A
3
B
3
3
3
C
C
C
C
C
C
C
0
0
0
0
0
Sanple
Description
Unit 1. 9/26. AM
Unit 1, 9/26. AM. Oup
Unit 1. 9/26. PN
Unit 2. 9/26. AM
Unit 2. 9/26. PM
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 3. 9/28, AM
Unit 3, 9/23. AM. Oup
Unit 3. 9/29. PM
Unit 4, 9/28. AM
Unit 4. 9/29. PM
FACILITY 8 AVERAGE
STANDARD DEVIATION
Unit 2. 9/28. PH
Unit 2, 9/29, PM
Unit 2. 9/29. PM. Oup
Unit 2. 9/30. AM
Unit 2, 9/30. PM
Unit 2, Coarse
Unit 2. Fine (ESP)
FACILTIY C AVERAGE
STANDARD DEVIATION
Unit 1-2, 10/3, AM
Unit 1-2. 10/3. AM, Oup
Unit 1-2. 10/3, PM
Unit 1-2. 10/4. AM
Unit 1-2, 10/4, PM
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
2.3.7,8
TOM
(ng/g)
0.093
0.11
0.13
0.24
0.22
0.16
0.06
0.38
0.38
0.63
0.24
0.13
0.35
0.17
2.2
l.S
2.1
2.4
1.5
<0.14
3.9
1.95
1.07
0.38
0.45
0.83
0.66
0.37
0.54
0.18
22
0.07
3.9
0.86
0.98
TETRA
-COO
(ng/g)
2.3
2.8
4.7
5.2
6.6
4.32
1.58
12
11
18
6.5
7.0
10.90
4.15
27
31
33
43
18
<0.14
38
27.2
13.3
5.2
5.1
19
11
7.9
9.64
5.15
22
0.07
43
14.3
12.2
PENTA
-COO
(ng/g)
11
14
20
16
32
18.60
7.31
139
114
137
84
99
114.60
21.34
238
710
722
513
335
<0.02
980
500
309
54
46
91
61
45
59.4
16.8
22
0.01
980
203
270
HEXA
-COO
(ng/g)
20
20
35
18
24
23.40
6.12
126
123
322
207
209
197
73
697
5565
3946
1430
1052
<0.03
3400
2299
1880
105
103
106
89
49
90.4
21.6
22
0.015
5565
802
1475
HEPTA
-COO
(ng/g)
14
14
26
14
14
16.40
4.80
100
93
203
352
435
237
136
331
1759
3030
1751
1089
<0.06
4900
1837
1559
45
48
81
39
37
50.0
16.0
22
0.03
4900
653
1199
OCTA
-COO
(ng/g)
17
18
31
13
11
18.00
6.99
96
39
210
586
1363
469
482
393
2460
3152
2338
1433
<0.16
2700
1782
1116
44
48
113
35
37
55.4
29.2
22
0.08
3152
690
1017
TOTAL
-COO
(ng/g)
64.J
68.8
116.7
66.2
87.6
80.7
19.8
473
430
890
1235.5
2113
1028
- 617
1686
10525
10883
6075
3927
0
12018
6445
4441
253.2
250.1
410
235
175.9
265
77.7
22
0
12018
2363
3775
4-18
-------
TABLE 4.7 PCOO AND PCOF IN SOLID SAMPLES
FLY ASH (FURAN HOMOLOGS)
Plant
Sample
Description
A Unit 1. 9/26, AM
A Unit 1. 9/26, AM. Oup
A Unit I. 9/26. PM
A Unit 2, 9/26, AM
A Unit 2. 9/26. PM
FACILITY A AVERAGE
STANDARD DEVIATION
B Unit 3, 9/28, AM
B Unit 3. 9/28, AM. Oup
3 Unit 3. 9/29, PM
B Unit 4, 9/28, AM
B Unit 4, 9/29. PM
FACILITY B AVERAGE
STANDARD DEVIATION
C Unit 2. 9/28. PM
C Unit 2, 9/29. PM
C Unit 2. 9/29. PM, Oup
C Unit 2, 9/30, AM
C Unit 2, 9/30. PM
C Unit 2, Coarse
C Unit 2. Fine (ESP)
FACILITY C AVERAGE
STANDARD DEVIATION
0 Unit 1-2. 10/3. AM
0 Unit 1-2, 10/3, AM, Oup
0 Unit 1-2. 10/3, PM
0 Unit 1-2, 10/4, AM
0 Unit 1-2. 10/4. PM
FACILITY D AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
2,3.7,8
TCDF
(ng/g)
0.66
26
13
13
2
0.66
26
13.33
12.6?
TETRA
-CDF
(ng/g)
20
23
34
52
39
43.6
25.3
91
97
107
48
59
80.4
22.3
61
164
169
130
73
3.3
110
102
55
36
36
93
70
53
57.6
21.7
22
3.3
169
73.6
43.2
PENTA
-CDF
(ng/g)
7.1
10
15
16
32
16.0
3.6
64
65
61
37
46
54.6
U.I
56
221
226
153
93
1.5
310
152
100
32
27
47
32
27
33.0
7.3
22
1.5
310
71.8
80.0
HEXA
-CDF
(ng/g)
17
14
23
96
13
33.6
31.3
56
61
241
41
54
90.6
75.5
54
336
2353
473
638
0.22
590
635
738
115
21
87
87
37
69.4
34.9
22
0.22
2353
246
496
HEPTA
-CDF
(ng/g)
14
12
22
44
9.9
20.4
12.5
40
40
19
49
63
42.2
14.3
10
32
77
666
610
<0.03
570
281
292
30
3.3
75
50
29
47.6
28.5
22
0.015
666
114
201
OCTA
-CDF
(ng/g)
2.1
2.3
4.0
1.4
2.0
2.4
0.9
8.1
3.3
21
11
34
16.5
9.9
24
60
362
108
175
<0.15
170
128
114
4.9
5.6
9.3
3.1
3.7
5.4
2.4
22
0.075
362
46
36
TOTAL
-CDF
(ng/g)
60.2
61.3
98
209.4
150.9
116.0
57.2
259.1
271.3
449
186
256
284
87.6
205
813
3187
1530
1589
5.52
1750
1297
1001
267.9
93.4
311.8
242.1
149.7
213
79.9
22
5.52
3187
552
765
TCOO r
TCDF
(ng/g)
124.5
13G.1
214.7
275.6
238.5
196.7
59.9
732.1
701.3
1339
1421.5
2369
1313
606
1891
11338
14070
7605
5516
5.52
13768
7742
5187
521.1
343.5
721.8
477.1
325.6
478
143
22
5.52
14070
Z915
4436
4-19
-------
TABLE 4.7 PCOO AND PCOF IN SOLID SAMPLES
COMBINED BOTTOM ASH AND FLY ASH (DIOXIN HOMOLOGS)
Plant
A
A
A
A
C
C
C
C
C
Unit 1. 9/26. AM
Unit 1, 9/26. PM
Unit 2. 9/26. AM
Unit 2, 9/26. PM
FACILITY A AVERAGE
STANOARO DEVIATION
Unit 2. 9/28. PM
Unit 2. 9/29. PM
Unit 2. 9/30, AM
Unit 2. 9/30. AM. Dup
Unit 2. 9/30. PM
FACILITY C AVERAGE
STANOARO DEVIATION
Unit 1-2, 10/3. AM
Unit 1-2, 10/3. PN
Unit 1-2, 10/4, AM
Unit 1-2. 10/4, PM
FACILITY 0 AVERAGE
STANOARO DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANOARO DEVIATION
2.3,7,8
TCDO
(ng/g)
0.02
0.07
0.33
0.14
0.14
0.12
0.13
0.62
0.78
<0.31
0.36
0.28
0.07
<0.08
<0.23
0.04
0.07
0.04
12
0.02
0.78
0.21
0.24
TETRA
-COO
(ng/g)
1.5-
2.2
13
5.57
5.26
2.2
2
14
13
1.3
6.50
5.73
1.3
0.46
<0.23
1.1
0.75
0.47
12
0.14
14
4.35
5.23
PENTA
-OX)
(ng/g)
2.7
3.2
19
a. 30
7.57
11
11
47
50
10
25.8
13.6
4
2.3
1.9
2.6
2.70
0.79
12
1.9
50
13.7
16.3
HEXA
-COO
(ng/g)
1.9
2
11
4.97
4.27
13
18
67
78
11
37.4
29.0
3.4
1.4
1.5
1.8
2.03
0.31
12
1.4
78
17.5
25.3
HEPTA
-COO
(ng/g)
1.7
1.5
3.2
3.80
3.11
15
31
120
120
22
61.6
48.0
3.3
1.4
1.5
1.6
1.95
0.78
12
1.4
120
27.3
42.5
OCTA
-COO
(ng/g)
0.89
0.34
3.7
1.31
1.34
7.7
18
89
39
18
44.3
36.7
2.6
1.4
1.3
1-2
1.63
0.57
12
0.34
39
19.5
31.7
TOTAL
-COO
(ng/g)
8.69
9.74
54.9
24.44
21.54
48.9
80
337
350
62.3
176
137
14.6
6.96
6.2
3.3
9.02
3.31
12
6.2
350
82.3
119
4-20
-------
TABLE 4.7 PCDO AND PCOF IN SOLID SAMPLES
COMBINED BOTTOM ASH AM) FLY ASH (FURAN HOMOIOGS)
Plant
A
A
A
A
C
C
C
C
C
0
0
0
0
t
Saopl*
J.3,7,8
TCOF
Description (ng/g)
Unit 1. 9/26, AM
Unit 1. 9/26, PM
Unit 2, 9/26, AM
Unit 2. 9/26. PH
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 2, 9/28, PN
Unit 2, 9/29, PM
Unit 2. 9/30, AM
Unit 2. 9/30, AM. Oup
Unit 2, 9/30, PM
FACILITY C AVERAGE
STANDARD DEVIATION
Unit 1-2. 10/3, AM
Unit 1-2. 10/3. PM
Unit 1-2, 10/4, AM
Unit 1-2. 10/4, PM
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
0.88
2.4
12
5.09
4.92
0.8
0.89
2.9
3.8
0.55
1.79
1.31
0.76
0.44
0.41
0.62
0.56
0.14
12
0.41
12
2.20
3.14
TETRA
-CDF
(ng/g)
6.3
20
91
39.10
37.12
5
4.7
20
24
3.4
11.42
8.75
5.1
3.1
2.3
3.4
3.48
1.02
12
2.3
91
15.69
23.90
PENTA
-CDF
(ng/g)
2.5
6.7
37
15.40
15.37
5.2
5.5
20
27
4.8
12.50
9.25
4.7
2
1.6
2.2
2.63
1.22
12
1.6
37
9.93
11.10
HEXA
-CDF
(ng/g)
1.3
3.2
18
7.50
7.47
6.4
11
24
•35
6.3
16.54
11.27
4.1
1.3
1.2
1.8
2.10
1.18
12
1.2
35
9.47
10.35
HEPTA
-CDF
OCTA
-CDF
(ng/g) (ng/g)
0.62
1.2
6.6
2.81
2.69
4.8
8
27
36
8.2
16.80
12.39
2.6
0.81
4.83
1.1
1.34
0.74
12
0.62
36
8.15
10.95
0.18
0.28
1.3
0.59
0.51
1.4
1.8
6.7
8.4
2.1
4.08
2.89
0.59
0.27
0.21
0.23
0.33
0.15
12
0.18
8.4
1.96
2.61
TOTAL
-CDF
(ng/g)
10.9
31.38
153.9
65.4
63.1
22.8
31
97.7
130.4
24.8
61.34
44.34
17.09
, 7.48
6.14
8.73
9.86
4.27
12
6.14
153.9
45.2
49.5
TCDD *
TCDF
(ng/g)
19.59
41.12
208.3
39.8
84.6
71.7
111
434.7
480.4
87.1
237
181
31.69
14.44
12.34
17.03
18.88
7.58
12
12.34
480.4
127
157
4-21
-------
TABLE 4.7 PCOO AND PCDF IN SOLID SAMPLES
BOTTOM ASH (OIOXIN HOMOLOGS)
Plant
3
8
B
B
3
Plant
B
B
B
a
B
Sanple
Description
Unit 3. 9/28. AM
Unit 3, 9/29, PM
Unit 4, 9/28. AN
Unit 4, 9/28. AM, Oup
Unit 4, 9/29. PM
FACILITY B AVERAGE
STANDARD DEVIATION
Samp]*
Description
Unit 3. 9/28, AM
Unit 3, 9/29. PM
Unit 4, 9/28. AM
Unit 4. 9/28. AM. Oup
Unit 4. 9/29, PM
FACILITY 8 AVERAGE
STANDARD DEVIATION
2.3.7.8
TCOO
(ng/g)
<0.04
<0.04
<0.08
0.01
<0.14
0.03
0.02
2.3.7,8
TCDF
(ng/g)
0.03
0.02
0.05
0.09
0.3
0.10
0.10
TETRA
-COO
(ng/g)
<0.04
<0.04
<0.08
0.11
0.65
0.17
0.24
BOTTOM ASH
TETRA
-CDF
(ng/g)
0.15
0.06
0.28
0.68
1.3
0.49
0.46
PENTA
-COO
(ng/g)
<0.01
<0.02
<0.05
0.21
2
0.45
0.78
(FURAN
PENTA
-CDF
(ng/g)
0.07
0.02
0.18
0.33
1.5
0.42
0.55
HEXA
-COO
(ng/g)
0.02
0.03
0.07
0.16
2.3
0.52
0.39
HOMOLOGS)
HEXA
-CDF
(ng/g)
0.02
0.05
0.1
0.26
2.5
0.59
0.96
HEPTA
-COO
(ng/g)
0.09
0.13
0.13
0.24
6.3
1.38
2.46
HEPTA
-CDF
(ng/g)
0.04
0.03
0.1
0.26
6.9
1.47
2.72
OCTA
-COO
(ng/g)
0.16
0.16
0.35
0.61
29
6.06
11.47
OCTA
-CDF
(ng/g)
<0.04
<0.04
0.06
0.12
3.7
0.78
1.46
TOTAL
-COO
(ng/g)
0.27
0.32
0.55
1.33
40.25
8.54
15.36
TOTAL
-CDF
(ng/g)
0.28
0.16
0.72
1.65
15.9
3.74
6.10
TCDO +
TCDF
(ng/g)
0.55
0.48
1.27
2.98
56.15
12.29
21.95
4-22
-------
TABLE 4.7 PCOO AND PCOF IN SOLID SAMPLES
LANDFILL COMPOSITE (DIOXIH HOHOLOGS)
2.3.7.8 TETRA PEHTA HEXA HEPTA OaA TOTAL.
Sample TCDO -COO -COO -COO -COO -COO -COO
Plant Description (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
C Perimeter Composite 0.07 1.2 5.7 6.3 9 6.1 28.8
0 Perimeter Composite 0.15 2.5 6 4.1 4.2 3.9 20.7
LANDFILL COMPOSITE (FURAN HOHOLOGS)
2.3.7.3 TETRA PENTA HEXA HEPTA OCTA TOTAL TCOO *
Sample TCOF -CDF -COF -COF -COF -COF -COF TCOF
Plant Description (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
C Perimeter Composite 0.51 2.4 3.9 4 3.3 0.81 14.41 43.21
0 Perimeter Composite 1.3 11 7.7 5.3 2.7 0.61 27.31 48.01
4-23
-------
analyzed. This was expected because the chemical properties of the PCDD
compounds cause then to adhere strongly to the finest particles.
A review of the PCDF homolog concentrations in the fly ash again
showed that the variability between the shifts and units was relatively
small, while the concentration variability between facilities was
extremely large (i.e., the concentration standard deviations for the
homologs exceeded the average homolog concentrations). Facility C had the
highest concentration of total PCDFs, as well as the highest concentration
of each PCDF homolog, followed by Facility B, Facility D, and Facility A,
which had the lowest concentration of each ?CDF homolog. The hexa-CDF
homolog was the most prevalent at three facilities, and the second most
prevalent at the fourth facility. Similarly, the octa-CDF homolog was
the least prevalent at three facilities and, the second least prevalent
at the fourth facility. The tetra-CDF homolog was generally the second
most prevalent, with the exception of Facility C where it was the least
prevalent. As was the case for the PCDDs, the hexa- through octa-
chlorinated classes of PCDFs increased disproportionately as the total
PCDFs increased.
As was the case for the PCDDs, two discrete fly ash fractions from
Facility C were analyzed for PCDFs. Again, the coarse fly ash fraction
contained a minimal quantity of PCDFs, but the fine fly ash fraction
exhibited the highest concentrations of PCDF homologs found in any fly
ash sample. This was again anticipated because the PCDF compounds,
acting similarly to the PCDD compounds, adhere strongly to the finest fly
ash particles.
Upon comparing the concentrations of PCDDs with PCDFs in the fly
ash, the following observations were noted. First, the total
concentrations of PCDDs and PCDFs followed the same sequence of abundance
among the facilities (i.e., the total concentrations of both PCDDs and
PCDFs increased in the order: Facility A - Facility D - Facility B -
Facility C). Second, the production of the hexa-chlorinated classes of
PCDDs and PCDFs was favored at each of the four facilities. Third, the
4-24
-------
penta- and/or hepta-chlorinated classes of both PCDD and PCDF are never
the most or least abundant. Finally, there does not appear to be any
correlation between the relative abundances (i.e., percentage) of PCDOs
or PCDFs in the total PCDD/PCDF concentrations.
A review of the PCDD homolog concentrations in the combined
bottom/fly ash and bottom ash showed that the variability between shifts
and units was relatively small compared to the variability between
facilities. However, some trends for the variabilities between shifts
and units were observed. At Facility A, variability between units was
very small (i.e., the PCDD concentrations of the ash from the different
units was essentially equal), but the PM shift samples contained higher
PCDD concentrations than the AM shift samples. Similarly, at Facility B
the PM shift samples exhibited higher PCDD concentrations than the AM
shift samples, but at Facility B, the units also showed a difference with
the samples from Unit 4 consistently having higher PCDD concentrations
than those from Unit 3. At Facility C. the AM shift samples showed
higher PCDD concentrations than the PM shift samples. Finally, at
Facility D, the variability was very small without any notable trends
between shifts.
As was the case for the fly ash. Facility C combined ash samples had
the highest concentrations of individual PCDD homologs as well as total
PCDDs. The samples from Facility A had the second highest PCDD concentra-
tions, followed by the samples from Facilities D and B, sequentially.
There was not any notable trends for the relative abundances of the
individual PCDD homologs. For example, the penta-CDD homolog was the most
abundant for Facilities A and D, while the octo-CDD and hepta-CDD homologs
predominated at Facilities B and C, respectively. Similarly, the least
abundant homolog was tetra-CDD for Facilities B, C, and D; however, the
octa-CDD homolog, which was the most abundant at Facility B, was the
least abundant at Facility A. The 2,3,7,8-TCDD isomer concentrations
were very low for all four facilities, usually being only slightly above
the detection limit.
4-25
-------
A review of the PCDP homolog concentrations in the combined
bottom/fly ash and bottom ash samples indicated that the variability
between shifts and units was relatively large, and that the variability
between facilities was extremely large. At Facility A, the samples from
Unit 2 had higher PCDF concentrations than the samples from Unit 3, and
the samples collected during the PM shifts had higher concentrations of
PCDFs than those from the AM shifts. Similarly, at Facility B the Unit 4
samples exhibited higher PCDFs than the Unit 3 samples, and the PM shift
samples contained more PCDFs than the AM shift samples. However, at
Facility C, the AM shift samples contained five times more PCDFs than the
PM shift samples. Finally, at Facility D the PCDF concentrations for the
samples from each shift were essentially equal.
The combined ash samples from Facilities A and C had the highest
concentrations of PCDFs and were approximately equal and were seven times
lower than corresponding concentrations from Facilities A and C. The
octa-CDF homolog was the least prevalent for three of the facilities;
however, it was the second most abundant homolog for Facility B. This
difference may be attributed to the Facility B sample consisting .
exclusively of bottom ash, while the samples from the other three
facilities consisted of combined bottom/fly ash. The tetra- and
hepta-CDF homologs predominated, each being the most abundant homolog at
two facilities. The concentrations of the penta- and hexa-CDF homologs
were approximately equal, and these homologs were never the most or least
abundant at any facility. The 2,3,7,3-TCDF isomer accounted for 15 to
20 percent of the total tetra-CDF homologs.
Upon comparing the PCDD and PCDF concentrations in the combined and
bottom ash, the following observations were noted. First, the
variabilities between shifts and units followed the same patterns for
PCDDs and PCDFs. Second, there was not any correlation between the most
abundant or least abundant for PCDDs and PCDFs. That is, while the
tetra-CDF homolog was the most abundant PCDF, the tetra-CDD homolog was
the least abundant PCDD. One notable trend concerning the homologs was
4-26
-------
that the hexa-CDD and haxa-CDF homologs were never the most or least
abundant. Third, as the total PCDDs increased, so did the total PCDFs.
Consequently/ the facilities that had the biggest concentrations of PCDDs
had the highest concentrations of PCDFs, and this was also true for the
facilities with the lowest concentrations. Finally, as was the case for
the fly ash, there was not an apparent correlation or trend between the
relative abundances of PCDDs or PCDFs in the total PCDD/PCDF
concentrations.
A review of the landfill composite sample results for PCDDs showed
that Facilities C and D were approximately equal. The tetra-CDD homolog
was the least abundant at both facilities, and the hepta-CDD and
penta-CDD homologs were the most abundant at Facilities C and D,
respectively. The tetra-CDOs at each facility were approximately six
percent 2,3,7,8-TCDD.
The PCDF results of the landfill composite samples showed that
Facility D was two times higher than Facility C. The oqta-CDF homolog
was the least "prevalent at each facility, and the hexa-CDF and tetra-CDF
homologs were the most prevalent at Facilities C and D, respectively.
There did not appear to be any trends concerning the concentrations of
2,3,7,8-TCDF, or the relative abundances of PCDD or PCDF in the total
PCDD/PCDF concentrations.
Upon comparing the PCDD and PCDF results of the combined bottom/fly
ash with the landfill perimeter composite samples from Facilities C
and D, it was noted that the combined ash from Facility C contained six
times more PCDDs and four times more PCDFs than the landfill composite.
Conversely, at Facility D, the landfill composite sample contained two
times more PCDDs and five times more PCDFs than the combined ash
samples. The first observation indicates that the landfill composite
sample at Facility C may have been biased by bottom ash, or that some of
the PCDDs and PCDFs may have already leached from the landfill. The
second observation suggests that the landfill composite sample at
Facility D may have been biased by fly ash, which contained significantly
4-27
-------
more PCDDs and PCDPs than the bottom or combined ash. Similarly, both of
these discrepancies may be attributed to the heterogeneity of the
combined ash and disposed ash (i.e., landfill composite) samples.
Upon comparing the PCDD and PCDF results of the fly ash with the
combined bottom/fly ash or bottom ash, the following observations were
noted. First, the variability between facilities for both fly ash and
combined/bottom ash PCDD and PCDF concentrations is extremely high. This
indicates that the feed material and/or incinerator conditions at the four
facilities are very different, resulting in the formation of significant
quantities of PCDD/PCDFs at one facility, and the formation of negligible
quantities of PCDD/PCDFs at another. Second, the variabilities between
shifts and units for both PCDDs and PCDFs in the combined/bottom ash are
greater than the corresponding variabilities for the fly ash. This
discrepancy is caused by the heterogeneicy of the combined/bottom ash
compared to the homogeneity of the fly ash. Third, the fly ash from
three facilities contained from three to forty times more PCDDs than the
combined ash, and the fly ash from Facility B contained 120 times more
PCDDs than the facility's bottom ash. This indicates that the PCDDs are
associated with the fine fly ash particles and PCDD concentrations in the
bottom ash are minimal. Therefore, the difference between the PCDD
concentrations in the fly ash and combined ash is caused by a bottom ash
dilution effect. Similarly, the fly ash from three facilities contained
from two to 25 times more PCDFs than the combined ash, and the fly ash
from Facility B contained 75 times more PCDFs than the facility's bottom
ash. Therefore, the difference between PCDF concentrations in the
combined ash and fly ash is a result of the dilution effect from the
bottom ash. Fourth, the tetra-CDD homologs are the least prevalent in
both the fly ash and the combined/bottom ash, while the hexa- through
octo- chlorinated classes of PCDDs are the most prevalent. This suggests
that the typical incinerator conditions favor the production of the more
highly chlorinated PCDD species. However, for both the fly ash and
4-23
-------
combined/bottom ash, the tetra- through hexa-chlorinated species of PCDFs
are the most abundant. This indicates that these same incinerator
conditions favor the formation of the lower chlorinated species of
PCDFs. Finally, the total concentrations of PCDDs and PCDFs in both fly
ash and combined/bottom ash followed the same sequence of abundance among
the facilities (i.e., the total concentrations of both PCDDs and PCDFs in
fly ash and combined ash increased in the order: Facility A - Facility D
- Facility B - Facility C).
4.3 Laboratory Leachates
One laboratory leachate composite sample of fly ash and one of
bottom/fly or bottom ash (plus 25 percent field duplicates) were
collected from each facility. These laboratory leachate composite
samples were representative of all combustion units and shifts during
which sampling was conducted.
The laboratory leachate composite samples from each facility were
subjected to three different leaching procedures in an attempt to
evaluate and compare the mobility of various constituents under different
extraction conditions.. The three different laboratory leaching
procedures were Extraction Procedure (EP), Toxicity Characteristic
Leaching Procedure (TCLP), and Mono-filled Waste Extraction Procedure
(MWEP; SW-924). The leachates prepared using these procedures were
analyzed for metals and organic constituents. Additionally, the leachates
prepared using TCLP were analyzed for PCDD/PCDF. The following sections
present the analytical results for each parameter summarized by sample
matrix, facility, and laboratory leaching procedure and a narrative
evaluation of these results.
4.3.1 Metals
The laboratory leachates prepared by EP, TCLP, and MWEP were analyzed
for cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), lead (Pb),
manganese (Mn), nickel (Ni), zinc (Zn), arsenic
-------
by sample matrix, facility, and leachate procedure in Table 4.3. The MWEP
method yielded two leachates from each laboratory leachate composite sample.
These leachates are listed in Table 4.8 as EX1 (i.e., Extraction 1) and EX2
(i.e., Extraction 2).
Upon reviewing Table 4.8, the following observations were noted.
First, the variability between leaching procedures and sample matrices
appears to be much .greater than the variability between facilities.
Additionally, because of this variability, there does not appear to be
any trends between the metal concentrations and the facilities. Second,
zinc, iron, lead, and manganese were present in the highest concentrations
in the leachates, while mercury was not present in any of the leachates.
Third, the fly ash appeared to contain higher extractable quantities of
cadmium and zinc than the bottom/fly and bottom ash, however the
extractable quantities of chromium, iron, and lead in the bottom/fly and
bottom ash were higher than in the fly ash. Finally, the extractable
quantities of copper, manganese, nickel, arsenic, mercury, and selenium
were essentially equal in the fly ash and the bottom/fly or bottom ash.
Upon comparing the different extraction procedures, the following
observations were noted. First, the EP and TCLP extraction methods were
much more aggressive than the MWEP for leaching every metal, except
selenium. In fact, the MWEP method was the only extraction procedure
which leached selenium. Second, none of the extraction methods leached
mercury. Third, the EP method appeared to extract copper and zinc more
vigorously than the TCLP method, while the TCLP method extracted
chromium, iron, manganese, nickel, and arsenic more aggressively than the
EP method. In fact, the TCLP method was the only one to extract
arsenic. Fourth, the extraction efficiencies of EP and TCLP were
approximately equal for cadmium, lead, and zinc. Finally, the
concentrations of metals in SW924-EX1 were generally greater than those
in SW924-EX2.
4-30-
-------
TABLE 4.3 EXTRACTABLE METALS DATA FOR THREE LABORATORY LEACHING PROCEDURES
Leachate
Procedure
EP Tox
Tap
SH924-EX1
SW924-EX2
EP Tox
TaP
SH924-EX1
SH924-EX2
EP Tox
TCLP
SM924-EX1
SW924-EX2
EP Tox
TttP
SW924-EX1
SW924-EX2
EP Tox
EP Tox
Tap
Tap
SM924-EX1
SH924-EX1
SW924-EX2
SW924-EX2
£P Tox
Tap
SW924-EX1
SW924-EX2
EP Tox
TCLP
SW924-EX1
SW924-EX2
EP Tox
EP Tox
TCLP
TCLP
SM924-EX1
SW924.EX1
SW924-EX2
SW924-CX2
Facility
A
A
A
A
c
c
c
c
0
0
0
0
B
B
3
a
A
A
A
A
A
A
A
A
3
3
3
3
C
C
C
c
0
0
0
0
0
0
0
0
Sample
Matrix
Bottom/Fly
Bottom/Fly
aottom/ny
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Sottom/Fly
Bottom/Fly
Sottom/Fly
Bottom/Fly
Bottom
Bottom
Bottom
Bottom
Fly
Fly (Oup.)
Fly
Fly (Oup.)
Fly
Hy (Oup.)
Fly
Fly (Dup.)
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Hy (Dup.)
Fly
Fly (Oup.)
Fly
Fly (Oup.)
Fly
Fly (Oup.)
Cd
ng/L
0.327
0.682
<0.01
-0.01
0.060
3.32
«0.01
<0.01
0.649
0.025
<0.01
<0.01
0.368
0.418
<0.01
<0.01
6.02
7.72
0.015
0.032
«0.015
<0.01
<0.01
<0.01
18.0
17.2
<0.01
0.033
7.39
3.36
0.122
<0.01
3.60
9.18
10.3
3.90
0.015
<0.01
<0.01
<0.01
Cr Cu Fe
mg/L mg/L mg/L
0.016 1.19 4.50
0.096 0.019 60.6
<0.005 <0.005 <0.005
«0.005 «0.005 <0.005
0.0059 0.039 143
<0.005 0.0076 23.4
-------
TABLE 4.3 EXTRAaABLE METALS DATA FOR THREE LABORATORY LEACHING PROCEDURES
Leactiatt
Procedure
EP Tox
Tap
SH 924
Extract 1
SH 924
Extract 2
EP Tox
TCLP
SH 924
Extract I
SM 924
Extract 2
Sample
Type
Combined
Bottom/
Fly Ash
Combined
Bottom/
Fly Ash
Combined
Bottom/
Fly Ash
Combined
Bottom/
Fly Ash
Fly Ash
Fly Ash
Fly Ash
Fly Ash
Sumary
Statistics
Mln.
Max.
Avg.
Std Oev
Mln.
Max.
Avg.
Std Oev
M1n.
Max.
Avg.
Std Oev
M1n.
Max.
Avg.
Std Oev
Min.
Max.
Avg.
Std Oev
Mln.
Max.
Avg.
Std Oev
M1n.
Max.
Avg.
Std Oev
H1n.
Max.
Avg.
Std Oev
Cd
mg/L
0.06
0.827
0.481
0.289
0.025
3.32
1.111
1.296
0.005
0.005
0.005
0.000
0.005
0.005
0.005
0.000
6.02
18
9.568
3.395
0.015
17.2
7.468
6.006
0.005
0.122
0.027
0.043
0.005
0.033
0.010
0.010
.Cr
mg/L
0.0059
0.15
0.051
0.058
0.0025
0.439
0.135
0.130
0.0025
0.005
0.003
0.001
0.0025
0.0025
0.003
0.000
0.0025
0.038
0.008
0.013
0.0025
0.544
0.217
0.218
0.0025
0.114
0.035
0.042
0.0025
0.15
0.047
0.061
Cu
mg/L
0.039
1.19
0.352
0.485
0.0025
0.019
0.012
0.007
0.0025
0.07
0.026
0.026
0.0025
0.009
0.004
0.003
0.041
1.62
0.377
0.561
0.0025
0.201
0.070
0.072
0.0025
0.089
0.029
0.031
0.0025
0.012
0.005
0.004
Fe
mg/L
4.5
143
58.725
53.577
0.328
60.5
34.407
23.338
0.0025
0.038
0.311
0.015
0.0025
0.024
0.013
0.008
0.0025
0.49
0.096
0.177
0.0025
190
42.004
67.172
0.0025
0.167
0.041
0.061
0.0025
0.118
0.031
0.044
Pb
mg/L
2.09
34
16.038
12.419
0.655
30.1
13.539
11.032
0.025
C.063
0.035
0.016
0.025
0.025
0.025
0.000
4.72
25.2
16.237
6.654
0.025
15.2
3.216
6.029
0.025
0.128
0.044
0.038
0.025
0.148
0.053
0.046
Hn
mg/L
3.6
6.24
4.525
1.014
4.2
11.9
7.525
2.775
0.0005
0.0021
0.001
0.001
0.0005
0.0012
0.001
0.000
2.71
8.03
6.058
1.837
0.049
14.7
7.013
5.315
0.0005
0.014
0.005
0.004
0.0005
0.0052
0.002
0.002
Nl Zn
mg/L mg/L
0.241 38.5
0.415 726
0.311 221.150
0.071 291.610
0.346 23.3
0.305 373
0.549 133.325
0.168 139.706
0.0075 0.0015
0.0075 0.067
0.008 0.018
0.000 0.028
0.0075 0.0031
0.0075 0.051
0.008 0.019
0.000 0.020
0.137 186
1.92 726
0.570 404.000
0.611 171.624
0.0075 0.151
1.52 746
0.521 361.459
0.498 271.582
0 0.026
0.022 1.22
0.009 0.256
0.007 0.435
0.0075 0.0015
0.0075 1.2
0.008 0.221
0.000 0.439
As
mg/L
0.005
0.005
0.005
0.000
0.005
0.037
0.017
0.013
0.005
0.005
0.005
0.000
0.005
0.005
0.005
0.000
0.005
0.005
0.005
0.000
0.005
0.111
0.045
0.040
0.005
0.005
0.005
0.000
0.005
0.005
0.005
0.000
Hg Se
mg/L mg/L
0.004 0.025
0.004 0.025
0.004 0.025
0.000 0.000
0.004 0.0025
0.004 0.025
0.004 0.019
0.000 0.010
0.01 0.0025
0.01 0.025
0.010 0.011
0.000 0.009
0.01 0.0025
0.01 0.0025
0.010 0.003
0.000 0.000
0.004 0.025
0.004 0.025
0.004 0.025
0.000 0.000
0.004 0.0025
0.004 0.025
0.004 0.017
0.000 0.009
0.01 0.0025
0.02 0.108
0.012 0.039
0.004 0.034
0.01 0.0025
0.01 0.0125
0.010 0.009
0.000 0.005
4-32
-------
TABLE 4.8 EXTRACTABLE METALS DATA FOR THREE LABORATORY LEACHING PROCEDURES
LEGEND:
EP TOX • EP TOXICITY extraction procedure
TO? - TOTAL CHARACTERISTIC LEACHATE PROCEDURE
SW 924 - Procedure for estimating monofllled solid waste leachate composition
SW 924 EX1 - First extract using SM 924 procedure
SW 924 EX2 • Second extract (on the sane sample) using SM 924 procedure
Bottom/Fly • combined bottom ash and fly ash samples
Fly - Fly ash
Bottom • Bottom ash
Oup. - Duplicate (split) of the previous sample
4-33
-------
4.3.2 Polychlorinated Dibenzo-p-dioxins and Polychlorinated
• Dibenzo-furans
The laboratory leachata samples prepared by TCLP were analyzed for
PCDD and PCDP homologs in the tetra- through octa-chlorinated classes.
Additionally, the 2,3,7,8-TCDD and 2,3,7,8-TCDF isomers were identified
and quantified. The results of these analyses are summarized by facility
in Table 4.9.
A review of the PCDD and PCDF concentrations in the TCLP-prepared
leachates showed that the extracted concentrations of PCDDs and PCDFs
were approximately equal. Only the hepta-CDD and octa-CDD homologs were
detected in two fly ash leachates (Facilities A and B), and only the
octa-CDD homolog was detected in one bottom ash leachate (Facility B).
Similarly, the hepta-CDF and octa-CDF homologs were detected in one fly
ash leachate (Facility B), while only the hepta-CDF homolog was detected
in the Facility A fly ash leachate. The octa-CDF homolog was detected in
only one bottom ash leachate (Facility B). Because the solid samples
contained significantly more PCDD and PCDF homologs than the
TCLP-prepared leachates, these observations indicate that the TCLP method
is inefficient for extracting (i.e., leaching) PCDD and PCDF compounds in
a waste ash matrix. Furthermore, they indicate that only the highly
chlorinated PCDD and PCDF species (i.e., hepta- and octa) tended to be
extracted by TCLP.
4.3.3 Organic Constituents
The laboratory leachates prepared by EP, TCLP, and SW-924 (MWEP)
were analyzed for organic constituents (i.e., organic scan and BNAs).
Additionally, the leachates prepared by MWEP were analyzed for TOC. The
results of these analyses are summarized by facility and extraction
procedure in Table 4.10. The numerical code appearing with each organic
constituent name represents the CAS designation for that compound.
4-34
-------
TABLE 4.9 PCM AND PCOf IN LABORATORY LEACHATE SAMPLES (TCLP)
OIOXIN HONOLOGS
2,3,7,8 TETRA PEHTA HEXA HEPTA OCTA TOTAL
Sanpl* Sanple TCOO -COO -COO -CDO -COO -COO -COO
Plant Matrix Description (ng/1) (ng/1) (ng/1) (ng/1) (ng/1) (ng/1) (ng/1)
A Bottom/Fly Unit 2. 9/26, AN
A Fly Unit 2. 9/26, AN
Bottom
Fly
C Bottom/Fly
C Fly
Bottom/Fly
Fly
Sample
Plant Matrix
A
A
B
B
C
C
0
0
Bottom/Fly
Fly
Bottom
Fly
Bottom/Fly
Fly
Unit 4, 9/28, AN
Unit 4, 9/28, AN
Unit 2, 9/29, PN
Unit 2, Coarse
Unit 1-2. 10/3, AN
Unit 1-2. 10/3, AM
Sanple
Description
Unit 2, 9/26, AN
Unit 2. 9/26, AM
Unit 4, 9/28, AN
Unit 4, 9/28, AH
Unit 2, 9/29, PN
Unit 2. Coarse
Bottom/Fly Unit 1-2, 10/3, AM
Fly Unit 1-2, 10/3, AN
<0.038 <0.038 <0.023 <0.018 <0.028 <0.035 0
-------
TABLE 4.10 EXTRACTABLE ORGANICS DATA FOR THREE LEACHING PROCEDURES
EP Toxldty
lant
A
A
A
a
3
C
C
0
0
0
Sample
Matrix
Bottom/ Fly
Fly
Hy (Oup)
Bottom
Fly
Bottom/Fly
Fly
Bottom/Fly
Fly
Fly (Oup)
Organic
Scan
(mg/1)
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.25
<0.2S
<0.25
TOTAL NUMBER FOUND
BNA
Peaks
Found
(No.)
5
33
Naphtti- Methyl Oletnyl- Dimethyl Methyoxy
alene Naphtha, phthalate pro'dlol Ethane Number of
91203 91576 34662 126307 74498887 Unknown
(ug/1) (ug/1) (ug/1) (ug/1) (ug/1) Organic*
8
18
16
13
IS
9
18
16
17
12
190
23
TCL?
BNA Dlethyl- Olbutyl- bis E.H. Methyoxy Methoxy Dimethyl
lant
A
A
A
B
B
C
C
0
0
0
Sample
Matrix
Bottom/ Fly
Fly
Fly (Dup)
Bottom
Fly
Bottom/ Fly
Fly
Bottom/Fly
Fly
Fly (Dup)
Organic
Scan
(ng/i)
6.9
<0.25
<0.2S
<0.25
<0.2S
<0.25
<0.25
<0.25
<0.25
<0.25
Peaks phthal. phthal.
Found 84662 847*2
(No.) (ug/1) (ug/1)
TOTAL NUMBER FOUND
12
21
17
14
14
12
90
21
11
16
13
10
12
phthal. Ethane
117817 74498887
(ug/1) (ug/1)
22
Ethanol Prop'dlol Number of
111773 126307 Unknown
(ug/1) (ug/1) Organic*
11
19
13
10
140
10
14
11
11
10
4-36
-------
TABLE 4.10 EXTRACTABLE ORGANICS DATA FOR THREE LEACHING PROCEDURES
SW 924 FIRST EXTRACTION
Plant
A
A
A
8
3
C
C
0
0
0
Plant
A
A
A
8
8
C
C
0
0
0
Sample
Matrix
Bottom/Fly
Fly
Fly (Oup)
Bottom
Fly
Bottom/Fly
Fly
Bottom/Fly
Fly
Fly (Oup)
TOTAL NUMBER
Sample
Matrix
Bottom/Fly
Fly
Fly (Oup)
Bottom
Fly
Bottom/Fly
Fly
Bottom/Fly
Fly
Fly (Oup)
TOC
(•9/1)
9.4
4.3
6.3
12.1
16.9
10.3
9.2
31
6.7
4.4
FOUND
Oleyl
Alcohol
143282
(ug/1)
83
SNA
Organic Peaks
Scan Found
(rag/1) (No.)
<0.25 11
<0.2S
<0.25
<0.25 23
<0.2S
<0.2S 10
<0.2S
<0.25 6
<0.25
<0.25
SO
Etnoxy Cycloocta
Ethanol Decane
929373 17455139
(ug/1) (ug/1)
310 580
150
Benzole Dlethyl-
Phenol Add ph thai ate
108952 65850 84662
(ug/1) (ug/1) (ug/1)
28 46
3
1 1 1
Methoxy M.Furan- SW 924
Ethane dlone Extr. 1
74498887 766392 Unknowns
(ug/1) (ug/1) (No.)
4
10 6 17
10
3
£., 01M Dimethyl
Oloxane pro'diol
25796263 126307
(ug/1) (ug/1)
Bis oxy
Ethanol
112276
510
96
160
TOTAL NUMBER FOUND
34
4-37
-------
TABLE 4.10 EXTRACTABLE ORGANICS DATA FOR THREE LEACHING PROCEDURES
SH 924 SECOND EXTRACTION
Plant
A
A
A
3
a
c
c
0
0
0
Sample
Matrix
Bottom/Fly
Fly
Fly (Oup)
Bottom
Fly
Bottom/Fly
Fly
Bottom/Fly
Fly
Fly (Oup)
SH 924
Extr. 2
TOC
(•9/1)
6.7
6.3
3.9
3.5
7.0
3.6
NA
NA
9.3
17.6
SH 924
Extr. 2
Org Scan
(ng/1)
<0.2S
<0.25
<0.25
<0.25
<0.2S
<0.25
<0.2S
<0.25
<0.2S
<0.25
SNA
Peaks
Found
(Ho.)
13
21
3
,
IS
Olethyl
Phenol phttial.
108952 34662
(ug/1) (ug/1)
33 3
E.hexyl Dimethyl
phthal. pro'dlol
117817 126307
(ug/1) (ug/1)
Methoxy
Ethanol
111773
(ug/1)
6
13
140
TOTAL NUMBER FOUND
57
Plant
B
B
C
C
0
0
0
Sample
Matrix
A Bottom/Fly
A Fly
A Fly (Oup)
Bottom
Fly
Bottom/Fly
Fly
Bottom/Fly
Fly
Fly (Oup)
Bis oxy Ethoxy Beru.DI Cycloocta
Ethanol Ethanol Carboxy.A decane
112276 929373 117828 17455139
(ug/1) (ug/1) (ug/1) (ug/1)
18
46
Phenoxy Oxahexa-
Ethanol decanol
2315619 23778521 Unknowns
(ug/1) (ug/1) (No.)
390
2 1200
950
17
13
15
TOTAL NUMBER FOUND
11
40
NOTE:
Names of organic constituents abbreviated ;
CAS numbers provided with constituent names
4-38
-------
The results for the EP-prepared leachates showed that the organic
scan did not detect any significant petroleum hydrocarbons in the samples
from any of the facilities. The results also showed that similar BNAs
were detected in samples from each facility with approximately equal
concentrations. Furthermore, every EP leachate that had a quantifiable
BNA contained diethylphthalate, which was the predominant SNA. Phthalate
esters, such as the one described, are common plasticizers which were
also noted in the laboratory leachate blank samples and therefore may
represent a background interference. The BNAs appeared to be slightly
more abundant in the bottom/fly ash than in the fly ash.
A review of the TCLP-prepared leachate results showed that gross
measurement of petroleum hydrocarbon content was in one organic scan
analysis (bottom/fly ash. Facility A). The other TCLP-prepared leachate
results showed the same trends described above for the EP-prepared
leachates.
The results presented in Table 4.10 for the SW-924 leachates showed
that there was not a predominant BNA compound. The results also
indicated that the bottom/fly ash and bottom ash contained slightly more
leachable BNAs than the fly ash. Finally, the results showed that there
was essentially no difference between the first and second SW-924
extractions.
Upon comparing the results from the three different leaching
procedures, the following observations were noted. First, the TCLP
method appears to be more efficient for extracting BNAs than the EP
method (i.e., 90 BNA constituents were detected in the TCLP leachates,
and only 33 BNAs were detected in the EP leachates). However, for the
compounds that were extracted by both procedures (e.g., diethyl-
phthalate), the concentrations were approximately equal. Second, the
extraction efficiency for SW-924 procedure appears to lie between the EP
and TCLP methods. However, the SW-924 procedure extracted totally
different classes of BNA constituents than the EP and TCLP methods.
Finally, for all three procedures, the combined bottom/fly ash and bottom
4-39
-------
ash contained slightly more BNAs than their corresponding fly ash.
suggesting that the BNA compounds are associated with the coarser,
heavier bottom ash materials or may be completely destroyed as the fly
ash passes through high temperature zones in the incinerator.
4.4 Field Water Samples
The field water samples collected from each facility included:
ground water, quench water, and field leachate. Each of these samples
were analyzed for total metals, PCBs. and BNAs. Additionally, the quench
water and field leachate samples were analyzed for PCDD/PCDFs. The
ground water samples were not analyzed for PCDD/PCDFs because these
materials generally absorb onto solid matrices which would not be
expected to migrate through the soil/ground-water interface. Sections
4.4.1 through 4.4.4 present the analytical results of each parameter for
these samples summarized by sample matrix and facility, and a narrative
evaluation of the results.
4.4.1 Metals
The field leachates, ground water, and quench water samples were
analyzed for total cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe),
lead (Pb), manganese (Mn), nickel (Ni), zinc (Zn), arsenic (As), selenium
(Se), and mercury (Hg). The results of these analyses were summarized by
sample matrix and facility and are presented in Table 4.11.
A review of the field leachate data in Table 4.11 showed that the
variability between samples at each facility, as well as the variability
between facilities, is relatively high. However, the variability between
samples at Facility D was lower than that at the other two facilities.
In general. Facility C leachates contained the highest concentrations of
metals, while the leachates at Facility B contained the lowest
concentrations of metals. Iron was the most prevalent metal tested,
while mercury and selenium were the least concentrated metals.
A review of the ground water data indicated that the variabilities
between samples and facilities were relatively small. Furthermore, the
4-40
-------
TABLE 4.11 TOTAL METALS DATA FOR FIELD WATER SAMPLES
FIELD LEACHATES
Facility
B
8
3
Sample
Description
Cast Sid*
North Sid*
Northeast Corner
FACILITY 3 AVERAGE
STANOARO DEVIATION
North Side
Northeast Corner
Northwest Corner
FACILITY C AVERAGE
STANOARO DEVIATION
Northeast Corner
Northeast Corner, Oup
Southeast Corner
FACILITY 0 AVERAGE
STANADARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANOARO DEVIATION
Cd
(mg/D
<0.010
<0.010
0.044
0.0180
0.0184
<0.010
<0.050
<0.010
0.0117
0.0094
0.031
0.023
<0.005
0.0188
0.0120
9
0.0025
0.044
0.0162
0.0142
Cr
(ng/D
<0.005
<0.005
0.024
0.0097
0.0101
0.011
0.914
0.0053
0.3101
0.4270
0.13
0.099
0.069
0.0993
0.0249
9
0.0025
0.914
0.1397
0.2773
Cu
(mg/L)
0.112
0.089
0.091
0.0973
0.0104
0.2
2.57
0.045
0.9383
1.1555
0.762
0.603
0.222
0.5290
0.2266
9
0.045
2.57
0.522
0.762
Fe
(
-------
TABLE 4.11 TOTAL METALS DATA FOR FIELD WATER SAMPLES
QUENCH WATER
Sample
Facility Description
A Unit 1. 9/26
A Unit 2. 9/26
FACILITY A AVERAGE
STANDARD DEVIATION
8 Unit 3, 9/28
3 Unit 4. 9/28
3 Unit 4, 9/28, Oup
FACILITY 8 AVERAGE
STANDARD DEVIATION
C Unit 2. 9/28
C Unit 2. 9/30
FACILITY C AVERAGE
STANDARD DEVIATION
0 Unit 2, 10/3
0 Unit 2. 10/3, Oup
0 Unit 2. 10/4
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
Cd
(mg/L)
0.065
0.114
0.0895
0.0245
<0.005
<0.005
<0.005
0.0025
0.0000
0.214
0.042
0.1280
0.0860
0.795
1.3
1.91
1.3350
0.4559
10
0.0025
1.91
0.4448
0.6369
Cr
(mg/L)
0.018
0.013
0.0155
0.0025
0.04
0.0085
0.0085
0.0190
0.0148
0.0098
0.014
0.0119
0.0021
0.408
0.646
1.12
0.7247
0.2959
10
0.0085
1.12
0.2286
0.3631
Cu
(mg/L)
0.117
0.253
0.185
0.068
0.02
0.048
0.041
0.0363
0.0119
0.066
0.064
0.0650
0.0010
2.51
3.36
13.1
6.4900
4.7064
10
0.02
13.1
2.008
3.906
Ft
(mg/L)
1.21
1.75
1.48
0.27
0.037
0.409
0.348
0.2647
0.1629
3.301
2
1.4005
0.5995
35
56.2
141
77.4000
45.7972
10
0.037
141
23.88
43.10
Pb
(mg/L)
4.07
5.94
S.005
0.935
0.176
0.274
0.264
0.2380
0.0440
0.213
0.289
0.2510
0.0380
19.1
27.8
37.9
28.2S67
7.6822
10
0.176
37.9
9.503
13.054
Mn
(mg/L)
0.144
0.127
0.1355
0.0085
0.024
0.082
0.079
0.0617
0.0267
' 0.6
0.34
0.7200
0.1200
7.47
12.6
10.6
10.2233
2.1112
10
0.024
12.6
3.257
4.712
N1
(mg/L)
<0.018
<0.018
0.009
0
<0.018
<0.018
<0.018
0.0090
0.0000
0.078
0.139
0.1085
0.0305
0.19
0.322
0.349
0.4537
0.2847
10
0.009
0.349
0.1623
0.2496
Zn
(mg/D
4.69
6.26
5.475
0.785
0.087
0.218
0.203
0.1693
0.0585
9.67
7.04
8.3550
1.315Q
64.6
132
192
129.53
52.04
10
0.087
192
41.68
64.26
AS
Se
(mg/L) (mg/L)
<0.010
0.017
0.011
0.006
<0.010
<0.010
<0.010
0.0050
0.0000
<0.010
<0.010
0.0050
0.0000
0.202
0.267
0.542
0.3370
0.1474
10
0.005
0.542
0.1058
0.1716
<0
<0
<0
<0
<0
0
0
<0
<0
0
0
<0
<0
<0
0
0
0
0
0
0
.0125
.0125
0.005
0
.0125
.0125
.0125
.0050
.0000
.0125
.0125
.0050
.0000
.0125
.0125
.0125
.0050
.0000
10
.0125
.0125
.0125
.0000
Hg
(rag/L)
0.0054
0.013
0.0117
0.0063
<0.0002
0.001
0.00099
0.0007
0.0004
0.00032
0.00032
0.0003
0.0000
0.022
0.02
0.0039
0.0153
0.0081
10
0.0001
0.022
0.0072
0.0086
4-42
-------
TABLE 4.11 TOTAL METALS DATA FOR FIELD HATER SAMPLES
GROUNOHATER
Facility Description
A *1
Cd Cr Cu F« Pb Hn HI Zn As S« Hg
(mg/L) (mg/L) (mg/L) (rag/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
-------
concentrations of metals in the ground water were almost negligible, with
only manganese and iron ever exceeding the 1 mg/L level. Mercury/ lead,
selenium, and nickel were not found in any ground water samples, and
cadmium and arsenic were found in only one sample, each. Iron was the
predominant metal detected, followed sequentially by manganese, zinc,
copper, chromium, arsenic, and cadmium.
A review of the quench water data showed that the variabilities
between shifts and/or units were very small, except for Facility 0 where
they were substantially higher. This observation was expected since the
quench water samples from Facility 0 contained much higher quantities of
solids than the samples from the other facilities. The variability
between facilities was relatively large. Facility D had the highest
concentration of every metal in the quench water, while Facility 3
had the lowest concentrations for nine out of the eleven metals. Iron
and zinc were the most concentrated metals in the quench water, followed
closely by lead, while mercury was the least concentrated metal.
Upon comparing the analytical results of the field leachates, ground
water, and quench water, the following observations were noted. First, the
quench water contained the highest concentration of metals, followed by
the field leachate and ground water, sequentially. Second, there did not
appear to be any correlation between the field leachate and ground water
data for any given facility. Third, the quench water and field leachate
results from Facility B are comparable, while the quench water metals
concentrations from Facility 0 are an order of magnitude higher than the
field leachate results. No similar trends for Facility C were observed.
Finally, although Facility B had the lowest metals concentrations in its
quench water and field leachate, it had the highest concentrations in its
ground water (no background metals data was available for comparison).
4.4.2 Polychlorinated Biphenyls
The field leachates, quench water, and ground water samples were
analyzed for individual PCB homologs and total PCBs. The results of
4-44
-------
these analyses are summarized by sample matrix and facility and are
presented in Table 4.12. A review of this table shows that only
negligible concentrations of PCBs were detected, with the highest total
PCS concentration for any sample being only 0.03 ug/L. Additionally,
only the three lowest chlorinated classes of PCBs (i.e., mono-, di-, and
tri-) were detected.
4.4.3 Polychlorinated Dibenzo-p-dioxins and Polychlorinated
Dibanzo-furans
The field leachate and quench water samples were analyzed for PCDDs
and PCDFs in the tetra- through octa-chlorinated classes. Additionally,
the 2,3,7,8-TCDD and 2,3,7,3-TCDF isomers were identified and
quantified. The results of these analyses are summarized by sample
matrix and facility in Table 4.13.
A review of the PCOO homolog concentrations in the field leachates
showed that the variabilities between samples at a given facility and
between facilities were both extremely high (i.e., the standard
deviations of the results exceeded the averages). Because the field
leachate samples at a given facility were collected within 100 to
200 feet of each other, this variability between samples at a given
facility was not anticipated. Two possible explanations for these
observed differences are (1) some of the samples appeared to be natural
seeps (i.e., "true" field leachate) that were turbid and expected to
contain more leachable constituents than the other samples, which
appeared to be surface water runoff, and (2) the heterogeneity of the
disposed ash materials may have caused "pockets" or areas of more highly
contaminated ash located in random areas of the landfill. The leachates
from Facility C contained the highest concentrations of PCDDs, and the
leachates from Facilities B and 0 had approximately equal PCOD
concentrations which were less than those from Facility C. The hepta-CDD
homolog was the most abundant, and the tetra-CDD homolog was the least
abundant. The 2,3,7,8-TCDD isomer accounted for 6 percent of the
tetra-CDD homologs and 0.4 percent of the total PCDDs.
4-45
-------
TABLE 4.12 PCBs IN FIELD WATER SAMPLES
FIELD LEACHATE
Plant
B
B
B
Sample
Description
MONO
-C8
ug/L
DI
-CB
ug/L
TRI
-•:B
ug/L
TETRA
-CB
ug/L
PENTA
-CB
ug/L
TOTAL
PCB
ug/L
East Side
North Sldt
Northeast Corner
C North Side
C Northeast Corner
C Northwest Corner
0 Northeast Corner
0 Northeast Corner, Oup
0 Southeast Corner
NUMBER OF PCBs FOUND
0.302
0.008
1
0
0
0
0.002
0
0
0
0
0.008
GROUNOWATER
Plant
C
C
C
C
Sample
Description
#4
Production Well
NUMBER OF PCBs FOUND
MONO
-CB
ug/L
01
-CB
ug/L
TRI
-CB
ug/L
TETRA
-CB
ug/L
PENTA
-CB
ug/L
TOTAL
PCB
ug/L
0
0
0
0
4-46
-------
TABLE 4.12 PCBs IN FIELD WATER SAMPLES
QUENCH HATER
Plant
A
A
B
3
B
C
c
0
0
0
Sampl*
Description
Unit i, 9/26
Unit 2. 9/26
Unit 3. 9/28
Unit 4, 9/28
Unit 4, 9/28. Oup
Unit 2. 9/28
Unit 2. 9/30
Unit 2. 10/3
Unit 2. 10/3, Oup
Unit 2, 10/4
MONO 01 TRI TETRA PENTA TOTAL
-C8 -CB -CB -CB -C8 PCS
ug/L ug/L ug/L ug/L ug/L ug/L
0
0.004 ' 0.004
0
0
0.03 0.03
0
0.02 0.02
0
0
0
NUMBER OF PCBs FOUND
4-47
-------
TABLE 4.13 PCDO AND PCDF IN FIELD WATER SAMPLES
FIELD LEACHATE (DIOXIN HOMOLOGS)
Sanple
Plant Description
B
B
8
C
C
C
0
0
0
East Side
North Side
Northeast Corner
North Side
Northeast Corner
Northwest Corner
Northeast Corner
Northeast Corner, Oup
Southeast Corner
2.3.7.8
TCDO
(ng/D
<0.06
<0.48
0.28
<0.22
1.6
<0.05
<0.22
<0.26
TETRA
-COO
(ng/1)
<0.06
<0.48
6.6
<0.22
28
-------
TABLE 4.13 POM AND PCOF IN FIELD MATER SAMPLES
QUENCH MATER (DIOXIN HOHOLOGS)
Plant
A
A
B
3
C
C
0
0
0
Sanple
Description
Unit 1, 9/26
Unit 2. 9/26
Unit 4. 9/28
Unit 4. 9/28. Oup
Unit 2. 9/28
Unit 2. 9/30
Unit 2. 10/3
Unit 2, 10/3, Oup
Unit 2. 10/4
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
2.3.7.8
TCDO
(ng/1)
<0.08
<0.08
<0.07
<0.07
<0.17
<0.81
8.2
17
1
9
0.035
17
2.98
5.55
TETRA
-COO
(ng/1)
0.1
2
<0.07
<0.07
<0.17
0.59
190
700
24
9
0.035
700
102
219
PENTA
-COO
(ng/D
0.82
4
«0.03
<0.05
0.26
5.9
610
650
30
9
0.015
650
150
258
HEXA
-COO
(ng/1)
0.66
2
<0.01
<0.04
1.1
10
500
450
72
9
0.005
500
115
194
HEPTA
-COO
(ng/D
0.58
1.9
<0.03
0.05
1.5
19
450
420
77
9
0.015
450
108
177
OCTA
-COO
(ng/1)
0.43
0.98
0.06
0.13
1.2
12
250
330
53
9
0.06
330
72
119
TOTAL
-COO
(ng/D
2.59
10.88
0.06
0.18
4.06
47.49
2000
2550
306
9
0.06
2550
547
937
QUENCH MATER (FURAN HOHOLOGS)
Plant
A
A
8
B
C
C
0
0
0
Sample
Description
Unit 1. 9/26
Unit 2. 9/26
Unit 4; 9/28
Unit 4. 9/28. Oup
Unit 2. 9/28
Unit 2. 9/30
Unit 2. 10/3
Unit 2. 10/3, Dup
Unit 2. 10/4
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
2.3,7,8
TCOF
(ng/1)
0.27
2.1
<0.06
<0.08
0.14
0.55
110
99
14
9
0.03
110
25.1
42.7
TETRA
-CDF
(ng/D
1.7
12
<0.06
<0.08
0.98
2.4
640
590
91
9
0.03
640
149
251
PENT*
-COF
(ng/1)
0.91
6.1
«0.01
<0.04
0.76
4
560
460
33
9
0.005
560
124
209
4-49
HEXA
.COF
(ng/D
0.51
3.1
<0.01
<0.02
0.61
6.2
490
390
31
9
0.005
490
108
131
HEPTA
-CDF
(ng/D
0.36
1.2
<0.02
0.04
0.52
6.5
310
280
59
9
0.01
310
73
120
OCTA
-CDF
(ng/D
0.27
0.27
<0.15
<0.30
0.25
1.4
75
68
16
9
0.075
75
18
29
TOTAL
-CDF
(ng/D
4.02
24.77
0
0.04
3.12
20.5
2075
1788
330
9
0
2075
472
790
TCDO *•
TCDF
(ng/D
6.61
35.65
0.06
0.22
7.18
67.99
4075
4338
636
9
0.06
4338
1019
1716
-------
The PCDF homolog concentrations in the field leachates again showed
that the variabilities between samples at a given facility and between
facilities were both extremely high. The leachates from Facility C
contained the highest PCDF concentrations, followed by the leachates from
Facilities B and 0, sequentially. The concentrations of the tetra-,
penta-, and hexa-CDF homologs were approximately equal, and these three
homologs were the most abundant. The octa-CDF homolog was the least
abundant. The 2,3,7,3-TCDF isomer accounted for 15 percent of the total
tetra-CDFs and 5 percent of the total PCDFs.
Upon comparing the results of the PCDDs with the PCDFs in the field
leachate samples, the following observations were noted. First, the
leachates from Facility C contained the highest concentrations of both
PCDDs and PCDFs, and the leachates from Facilities B and 0 contained
approximately equal concentrations of both PCDDs and PCDFs. Second, the
abundances of the tetra-CDD and tetra-CDF homologs appeared to be
inversely proportional (i.e., the least abundant PCDD homolog and the
most abundant PCDF homolog). Third, the abundances of the octa-CDD and
octa-CDF homologs also showed this inverse proportionality. Finally,
there did not appear to be any correlation between the relative
abundances of PCDDs or PCDFs in the total PCDD/PCDF concentrations.
The PCDD results for the quench water showed that the variability
between shifts and units was relatively small compared to the variability
between facilities. This suggests that the different combustion
conditions and feed materials at each facility contribute to this
variability. The quench water samples from Facility D contained the
highest PCDD concentrations, followed by the quench water samples from
Facilities C and B, sequentially. There did not appear to be any
correlations for the least or most abundant homologs, or for the
2,3,7,3-TCDD isomer.
A review of the PCDF concentrations in the quench water again showed
that the variability between shifts and units was relatively small
compared to the variability between facilities. The quench water from
4-50
-------
Facility D contained the highest PCDP concentrations, followed by the
quench water samples from Facilities C and B, sequentially. Again, there
did not appear to be any trends for the least or most abundant homologs,
or for the 2,3,7,8-TCDF isomer.
For quench water, comparing the PCDD results with the PCDF results
indicated the total concentrations of PCDOs and PCDFs followed the same
sequence of abundance by homolog among the facilities. However, there
were no correlations for the individual homologs, or for the relative
abundances of PCDDs or PCDFs in the PCDD/PCDF total concentrations.
Upon comparing the field leachate results with the results from the
quench water samples, the following observation was noted. The field
leachate samples from Facilities B and C contained more PCDDs and PCDFs
than the quench water samples from the facilities. However, the quench
water samples from Facility D contained 10 times more PCDDs and PCDFs
than the field leachate samples from this facility. This suggests that
the PCDDs and PCDFs at Facility D are readily leached from the solid ash
material in the quench water tank. Conversely, at Facilities B and C the
PCDDs and PCDFs appear to leach more slowly until the ash is disposed in
the landfill.
4.4.4 Organic Constituents
The field leachates, quench water, and ground water samples were
analyzed for organic constituents, including: TOC, organic scan, and
BNAs. The results of these analyzes are summarized by sample matrix and
facility in Table 4.14.
A review of the field leachate data showed that Facility D, had the
highest TOC and BNA constituent concentrations. Similarly, Facility B
had the lowest TOC and BNA constituent concentrations. The predominant
BNAs were thiolane, ethylhexyl phthalate, and dimethylpropanediol.
A review of the quench water data showed that the variabilities
between units and facilities were relatively large. Facility D had the
highest concentrations of TOC and BNA constituents, followed sequentially
4-51
-------
TABLE 4.14 ORGANIC CONSTITUENTS IN FIELD HATER SAMPLES
FIELD LEACHATES
Sample
Plant Description
a
8
3
C
C
C
0
0
0
East Side
Northeast Corner
North Side
Northwest Corner
Northeast Corner
North Side
Southeast Corner
Northeast Corner
Northeast Corner, Oup
No.
M1n.
Max.
Avg.
Std. Oev.
TOC
(mg/D
189.0
204.0
273.0
379.0
187.0
59.1
574.0
636.0
567.0
9
59.1
636
340.9
195.4
Organic
Scan
0«0/1)
<0.25
<0.25
<0.25
<0.25
2.5
<0.25
<0.25
<0.2S
8
0
2.5
NA
NA
Ethyl Dimethyl
SNA Hexyl Propane Hexa
Peaks Phthalate Dlol Blphenyl Thlepane Thlolane
Found 117817 126307 90437 17233715 289167
(No.) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L)
2
3
4
2
8
1
21
22
24
9
1
24
9.7
9.2
12
7
80
37
4
7
30
34.0
28.9
9
22
110
120
4
9
120
65.3
50.1
51
51
2
51
51
51.0
Q.O
82 400
140
1 2
82 140
32 400
82.0 270.0
0.0 . 130.0
Sanple
Plant Description
B East Side
3 Northeast Corner
3 North Side
C Northwest Corner
C Northeast Corner
C North Side
0 Southeast Corner
0 Northeast Corner
0 Northeast Corner, Oup
No.
Hln.
Max.
Avg.
Std. Oev.
Sulfo-
Benz- nylbls
aldehyde Sulfur
100527 67710
(ug/L) (ug/L)
1
8
8
8.0
0.0
11
1
11
11
11.0
0.0
Unknown
HCs Unknowns
(*) (#)
2
4
9
10
2
2
3
1
4
1
16
3
10
4-52
-------
TABLE 4.14 ORGANIC CONSTITUENTS IN FIELD HATER SAMPLES
QUENCH WATER
Plant
A.
A
B
B
B
• c
C
0
0
0
............
Saujjle
Description
Unit 2. 9/26
Unit 1. 9/26
Unit 3. 9/28
Unit 4, 9/28, Oup
Unit 4. 9/28
Unit 2. 9/28
Unit 2. 9/30
Unit 2, 10/3
Unit 2. 10/3, Oup
Unit 2. 10/4
NO.
M1n.
Max.
Avg.
Std. Dev.
TOC
(*B/1)
94.5
26.9
77.3
421.0
416.5
3.2
29.2
165.0
153.0
1228.0
10
3.2
1228
261.5
352.4
Organic
Scan
(•B/U
<0.25
<0.25
<0.25
<0.25
<0.25
12.3
<0.25
<0.25
<0.25
9
0.125
12.3
1.48
3.33
SNA
Peaks
Found
(No.)
29
8
23
20
20
5
25
25
25
9
5
29
20.0
7.7
Phenol
108952
(ug/L)
65
170
380
380
60
71
640
7
60
640
252.3
205.2
2 -Methyl
phenol
95487
(ug/L)
6
17
40
44
7
7
36
7
6
36
29.6
27.3
4-Methyl Dimethyl Benzole
phenol
106445
(ug/L)
92
94
23
3
23
94
69.7
33.0
phenol Acid
105679 65850
(ug/L) (ug/L)
36
260
300
2100
2100
570
900
44 3800
1 3
44 36
44 3800
44.0 1258.3
. 0.0 1219.0
Naphtha-
lene
91203
(ug/L)
3
1
8
8
8.0
0.0
Sample
Plant Description
A Unit 2, 9/26
A Unit 1, 9/26
B Unit 3, 9/28
8 Unit 4, 9/28, Dup
B Unit 4, 9/28
C Unit 2. 9/28
C Unit 2. 9/30
0 Unit 2. 10/3
0 Unit 2, 10/3, Dup
0 Unit 2, 10/4
Ethyl Methyl
Acenaph- Phenan- Butyl Fluor- Hexyl Butanoic Molecular
thylene threne Phthaiate anthene Pyrene Phthalate Acid Sulfur Thiolane
208968 35013 84742 206440 129000 117817 116530 10544500 289167
(ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L)
33
29
130
23
No.
M1n.
Max.
Avg.
Std. Oev.
1
6
6
6.0
0.0
1
6
6
6.0
0.0
1
3
3
3.0
0.0
4-53
1
6
6
6.0
0.0
1
5
5
5.0
0.0
1
8
8
8.0
0.0
1
33
33
33.0
0.0
2
29
130
79.5
50.5
1
23
23
23.0
0.0
-------
TABLE 4.14 ORGANIC CONSTITUENTS IN FIELD WATER SAMPLES
Plant
A
A
a
8
B
C
C
0
0
0
QUENCH HATER
Sanple
Description
Unit 2. 9/26
Unit 1. 9/26
Unit 3, 9/28
Unit 4, 9/28. Oup
Unit 4, 9/28
Unit 2. 9/28
Unit 2, 9/30
Unit 2. 10/3
Unit 2. 10/3. Oup
Unit 2. 10/4
No.
M1n.
Max.
Avg.
Std. Oev.
2-Hydrox
Benzole
Acid
69727
(ug/L)
40
SO
42
3
40
50
44.0
4.3
Hydroxy
Methyl
Pentenone
80717
(ug/L)
26
1
26
26
26.0
0.0
Pyran Hydroxy
Naphtho Methyl
01 one Pyranone
81845 118718
(ug/L) (ug/L)
6 11
130
1 2
6 11
6 130
6.0 70.5
0.0 59.5
Hydro Hexanoic
Pyranone Add
S42280 142621
(ug/L) (ug/L)
11 22
10
30
58
37
45
51
920
1 8
11 10
11 920
11.0 146.6
0.0 292.7
Methyl
Pentanolc Benz-
Acid aldehyde
646071 100527
(ug/L) (ug/L)
17 22
84
38
3 1
17 22
88 22
63.0 22.0
32.6 0.0
Methyl
Pentane-
diol
144194
(ug/L)
17
1
17
17
17.0
0.0
Sample
Plant
A
A
B
a
8
C
C
0
0
0
Description
Unit
Unit
Unit
Unit 4
Unit
Unit
Unit
Unit
Unit 2
Unit
2. 9/26
1. 9/26
3. 9/28
, 9/28, Oup
4. 9/28
2, 9/28
2. 9/30
2. 10/3
. 10/3. Oup
2. 10/4
Furan Benzene Tetra Methyl Benzene
Carfaox- Propanolc Oecanolc Purlne Acetic Oecanolc
aldehyde Add Add 01 one Acid Acid Unknown Unknown
67470 501520 544638 58082 103822 334485 Org Adds HCs Unknowns
(ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (#) (*) (I)
2 15
6
16
13
12
No.
Min.
Max.
Avg.
Std. Oev.
54
1
54
54
54.0
0.0
23
12
2
12
23
17.5
5.5
72 23
22
1 2
72 22
72 23
72.0 22.5
0.0 0.5
4-54
120
1
120
120
120.0
0.0
160
1
160
160
160.0
0.0
9
17
13
-------
TABLE 4.14 ORGANIC CONSTITUENTS IN FIELD WATER SAMPLES
GROUNONATER
Plant
A
' B
Sample
Description
SNA
Organic Peaks
TOC Scan Found
(iag/1) (mg/1) (No.)
#1
#2
3.4 <0.25
2.7 <0.25
No.
M1n.
Max.
Avg.
Std.
6
2
97.4
43.75
41.56
Ethyl
Hexyl
Phthalate
117817 Unknowns
(ug/L) (I)
c
c
c
c
#3
117
#4
Production Well
80.9
76.1
97.4
2.0
<0.2S
<0.2S
<0.2S
<0.2S
0
2
0
NOTE:
Names of organic constituents abbreviated:
CAS numbers provided with constituent names
4-55
-------
by Facilities B, A, and C. The predominant BNAs detected w«re benzole
acid, phenol, hexanoic acid, benzene acetic acid, and decanoic acid.
A review of the ground water data showed that the variability of the
TOG data between facilities was relatively high. Facility C had the
highest TOC concentrations, with Facilities A and B having approximately
equal concentrations significantly less than Facility C. Only one ground
water sample contained detectable quantities of BNA constituents -
Well 17 at Facility C. The only BNA positively identified was
bis-ethylhexyl phthalata.
Upon comparing the results from the different sample matrices, the
following observations were noted. First, the quench water contained the
highest quantities of BNA constituents, and the second highest quantity
of TOC. The field leachates contained the highest concentrations of TOC
and the second highest of BNA constituents. Second, there appeared to be
a slight correlation between TOC and BNA concentrations, however, there
did not appear to be any relationship between TOC or BNA and organic
scan. Finally, it was observed that certain BNA compounds were always
detected together. Phenol, methylphenol (phenolic derivatives), benzoic
acid, and hexanoic acid (carboxylic acids) were always found together, as
were naphthalene, acenaphthylene, phenanthrene, fluoranthene, and pyrene
(polycyclic aromatic hydrocarbons).
4.5 Quality Assurance/Quality Control Summary
The Versar laboratory and Versar's subcontract laboratory, Battelle.
Columbus, which conducted analyses for PCDDs and PCDFs, implemented
extensive quality control measures on all analyses. The procedures used
by the Versar laboratory conformed to the EPA Contract Laboratory Program
requirement*. During all analytical activities, quality control (QC)
samples were introduced into the sampling scheme in order to evaluate the
precision and accuracy of the analytical method. These QC samples
included laboratory-prepared QC samples (e.g., reagent blanks, duplicates,
matrix spikes, surrogate spikes, and check standards) and "blind" field
4-56
-------
duplicates (at a frequency of 25 percent per sampling plan
specifications)/ trip blanks, and field blanks. The field duplicate
samples were indicative of the precision of the entire sampling and
analysis method. The results of the QA/QC analyses are summarized in the
following subsections by major categories of analyses—total metals.
-PCBs, PCDD/PCDFs, and organic constituents. The original data reports
from the laboratories provide more extensive QC data and are included in
the appendices of this report. All data quality objectives and control
procedures were described in a QA Plan which was submitted to EPA for
review and approved prior to the initiation of chemical analysis.
4.5.1 Internal QA/QC
The internal QA/QC samples were prepared in the laboratory as
required by the analytical method to evaluate the performance of the
method. The following sections present the results and evaluations of
the internal QA/QC samples for metals, PCBs, PCDD/PCDFs, and organic
constituents.
4.5.1.1 Total Metals Analyses - Analyses of solid residues, field
water samples, and laboratory-prepared leachates for total metals were
performed by the Versar laboratory. Analyses of each sample batch for
each matrix (solid, field water, laboratory leachates) were accompanied
by internal QC checks consisting of the following analyses: reference
standard, calibration blank, one or two reagent blanks, a check standard
different from the reference standard, one sample duplicate selected at
random from the batch, and one spike. The standards were used to check
on the accuracy of calibration, the blanks are used to identify
contamination in reagents and laboratory water, the duplicates indicate
the precision or reproducibility of the analyses as the Relative Percent
Difference (RPD), and the spikes indicate the accuracy of analyses in
terms of the capabilities of the analyses to measure the constituent, or
percent recovery of any added spike.
The results of these internal QC cheeks for total metal analyses are
summarized in Table 4.15. The QC criteria for total metals analyses in
4-57
-------
TABLE 4.15 QC SUMMARY (INTERNAL) FOR METALS
ICP ANALYSES
AA ANALYSES
t ly Asn ana BOTIOM *sn
Olgestates
Reference Standard
Calibration Blank
Reagent Blank 1
Reagent Blank 2
Check Standard
Sanple Duplicate
(Sanple 17667)
Spike Recovery
Field water Saoples
(Ground Water a* Quench)
Reference Standard
Calibration Blank
Reagent Blank 1
Check Standard
Sanple Duplicate
(Sanple 19582)
Spike Recovery
Field water Samples
(GW & Field leachates)
UNITS
% Recovered
ug/L
ug/L
ug/L
* Recovered
%RPO
% Recovered
Cd
97.1
*10
*10
<10
95.7
4.3
(2)
Cr
97.4
<5
<5
<5
91.7
0.0
20.0
Cu
98.0
<5
<5
<5
92.5
5.2
(2)
Fe
103.1
<4
13
20
97.4
15.1
(2)
Pb
101.6
<50
<50
<50
93.3
4.4
(2)
Nn
95.7
<2
2.1
«2
91.4
4.6
(2)
Nt
92.9
<15
<15
<15
95.3
1.4
(2)
Zn
97.7
<3
4.2
9.5
95.0
3.9
(2)
ICP ANALYSES
UNITS
% Recovered
ug/L
ug/L
* Recovered
WPO
% Recovered
Cd
98.6
<10
<10
101.7
0.0
32.0
Cr
94.4
<5
8.9
98.0
(1)
35.1
Cu
95.5
<5
5.5
100.0
1.1
39.0
Fe
95.5
<4
27
98.5
67.7
36.3
Pb
98.6
<50
<50
98.4
(I)
79.5
Nn
95.0
<2
19
98.5
5.6
91.5
HI
96.0
<15
<15
102.0
(1)
33.5
Zn
99.5
«3
9.3
104.5
13.3
36.0
ICP ANALYSES
UNITS
Cd
Cr
Cu
Fe
Pb
Hn
N1
Zn
As
100.0
*10
<10
114.0
18.0
(2)
Se Hg
39.6 93.2
<5 <0.2
<5 <0.2
38.0 108.0
3.3 (I)
50.0 98.0
AA ANALYSES
AS
104.3
<10
<10
91.0
(1)
104.0
AA
AS
Se Hg
37.6 102.3
<5 <0.2
<5 <0.2
100.0 38.0
(1) (11
36.0 115.0
ANALYSES
Se Hg
Reference Standard
Calibration Blank
Reagent Blank 1
Check Standard
Saople Duplicate
(Sanple 19765)
Spike Recovery
* Recover* 98.2 94.8 93.5 93.5 103.6 94.0 95.0 99.5 106.5 35.7 97.7
ug/L <10 <5 <5 «5 <50 <1 <15 13 <10 <5 «0,I
ug/L <10 <5 44 21 <50
-------
TABLE 4.15 QC SUMMARY (INTERNAL) FOR METALS
Field Hater Samples
Batches 6
(Field Leachates)
UNITS
Cd
Cr
Cu
ICP ANALYSES
Fe Pb
Hn
N1
Zn
AA ANALYSES
As Se Hg
Reference Standard
Calibration Blank
Reagent Blank 1
Check Standard
Sample Duplicate
(Sample 19831)
Spike Recovery
% Recovered 97.4 96.3 100.0 98.0 108.1 98.5 106.0 100.5 115.2 37.S 97.7
ug/L <10 <5 <5 <5 <50
-------
TABLE 4.15 QC SUMtARY (INTERNAL) FOR METALS
SW - 924
1 extract 1 on n
Leachates
ICP ANALYSES AA ANALYSES
UNITS Cd Cr Cu Fe Pb Hn N1 Zn As Se Hg
Reference Standard
Calibration Blank
Reagent Blank 1
Reagent Blank 2
Check Standard
Sample Duplicate
(Sample 19517}
Spike Recovery
% Recovered 99.4 97.2 98.5 95.0 96.4 96.0 98.0 97.5 104.3 87.6 97.7
ug/L <10 <5 <5 <5 <50
-------
the project were an RPD between duplicate analyses of 0-20 percent, and
an accuracy (t recovery of spikes) of 75 to 125 percent in conformance to
the EPA Contract Laboratory Program.
No significant problems were encountered in maintaining calibration
or with contamination of reagents or laboratory water. Occasionally ,
some metals ware detected in calibration and reagent blanks in the low
microgram per liter (ug/L) range. Normally, no corrections of the sample
analytical results for the blanks w«re required.
The precision criteria (RPD on duplicates) were generally achieved
with some exceptions. In the analyses of field water samples, Fe
exceeded the criteria in analysis of Batches 1-4, Zn exceeded the
criteria in analysis of Batch 5, and Cu and Mn exceeded the criteria in
analysis of Batch 6. In the analyses of laboratory-prepared leachates,
the Versar laboratory encountered difficulty in achieving the criteria in
analyses for Cd, Cr, Cu, Fe and Ni in the EP leachate, Cd, Fe, Pb, Mn, Ni
and Zn in the TCLP leachate, and Mn, Zn, and Se in the first extract by -
the MWEP. The problems with the analysis of laboratory leachates may
have been related to the relatively low concentration levels for some of
•
these metals in 'the leachates and the inherent increased variability at
these low levels.
The accuracy criteria (% recovery of spikes) were also generally
achieved with few exceptions. In the analysis of the solid residue
digestates, the criteria for Cr was below the lower limit. In the
analyses of field water samples, the criteria for Pb was below the lower
limit in Batch 5, and the criteria for Cu and Pb were below the lower
limit in Batch 6. In the analyses of the laboratory-prepared leachates,
the criteria for Ni was below the lower limit in the EP leachates and the
TCLP leachates, the criteria for Cu, Zn and Se were below the criteria in
the first extract by the MWEP, and the criteria for Hg was slightly above
the upper limit in the second extract by the MWEP.
Overall, however, the analyses for total metals in all matrices were
in control. The data from the analyses of samples are, therefore.
4-61
-------
considered valid. Corrective actions were taken by the laboratory on
each occasion of a criteria exceedance in accordance with the Quality
Assurance Project Plan. These corrective actions maintained control in
the total metals analyses.
4.5.1.2 Polychlorinated Biphenyls - Analyses of solid residues and
selected field water samples for polychlorinated biphenyls (PCBs) were
conducted by the Versar laboratory. Samples were analyzed in three
separate groups at different times. The first group of samples consisted
of all fly ash samples collected at the four facilities. The second
group of samples consisted of selected field water samples including
quench water, leachates collected at the monofilled landfills, and ground
water. The third group of samples consisted of other ash samples
including bottom and combined bottom/fly ash, size fractions of fly ash
samples collected at Facility C, and composite samples collected from the
monofilled landfill at Facilities C and D. Analyses of each group
(except as noted below) were accompanied by internal QC checks consisting
of the following: (1) analysis of reagent blanks', (2) determination of
the recoveries of four isotopically-labeled (carbon ) isomers added as
surrogate spikes to all samples prior to extraction to track the
performance of the extraction, cleanup, and analysis of each sample, and
(3) determination of the recoveries of matrix spike (MS) and matrix spike
duplicates (MSD) on two field water samples. The MS and MSD consists of
a mixture of Arochlors 1016 and 1260 and are used to determine accuracy
and precision. No criteria for the recovery of surrogate spikes or for
the relative percent difference (RPO) between the matrix spikes and
matrix spike duplicates have been established for this method.
The results of these internal QC checks for the PCS analyses are
summarized in Table 4.16 and are discussed below.
No PCBs were detected in any of the laboratory reagent blanks
accompanying each group of samples analyzed, indicating that the
laboratory water and reagents were free of PCS contamination.
4-62
-------
TABLE 4.16 QC SUMMARY (INTERNAL) FOR PCB ANALYSIS
Surrogate Recovery (%)
Facility
A
A
A
A
A
A
A
A
A
A
A
A
A
A
a
3
B
3
3
3
3
a
3
a
a
a
3
8
B
a
a
a
a
a .
Sa*>le
Matrix
Fly
Fly
Fly
Fly
Fly
Bottom/Fly
8ottOfll/Fly
3ottoa/Fly
Bottom/Fly
Bottom/Fly
Bottoa/Fly
Bottoa/Fly
Quench
Quench
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Bottom
Botto»
Botton
8otto»
Bottom
Quench
Quench
Quench
Hacftate
leachate
leachate
LMChate
Letchate
Sample
Description
Unit 1, 9/26, AN
Unit 1. 9/26. AM, Oup
Unit 1. 9/26, PM
Unit 2. 9/26, AM
Unit 2, 9/26, PM
Unit 1. 9/26, AM
Unit 1, 9/26, PM
Unit 1. 9/26. PM
Unit 1, 9/26, PN
Unit 2, 9/26, AM
Unit 2, 9/26, AM, Oup
Unit 2. 9/26, PM
Unit 1. 9/26
Unit 2. 9/26
Unit 3, 9/28, AM
Unit 3, 9/28. AM, Oup
Unit 3, 9/29, PM
Unit 4, 9/28, AM
Unit 4. 9/29, PM
Unit 4, 9/29. PM
Unit 4, 9/29, PM
Unit 3. 9/28. AM
Unit 3, 9/29, PM
Unit 4. 9/28. AM
Unit 4, 9/28, AM, Oup
Unit 4. 9/29, PM
Unit 3. 9/28
Unit 4, 9/28
Unit 4. 9/28. Oup
East Side
North Side
Northeast Corner
Northeast Corner
Northeast Corner
Sanple
Nutter
17628
17631
17637
17643
17646
17625
17640
17640MS
17640MSO
17619
17622
17634
17546-47
17556-57
17669
17672
17693
17680
17686
17686MSO'
17686MS
17666
17690
17674
17677
17683
17596-97
17606-47
17536-37
19837-38
19859-60
19846-47MSO
19846-47MS
19846-47
4-Chloro-
Biphenyl
3
0
0
9
1
51
64
57
48
54
66
67
74
52
0
0
3
0
0
3
0.3
59
65
34
60
71
56
74
98
59
66
54
56
55
3,3'.4,4' Octa
Tetrachloro Chloro
Blphenyl Blphenyl
0
1.4
4
9
0
69
105
94
75
68
76
32
90
71
0
0
1
0.3
0
3
0
34
76
48
75
78
71
94
111
34
98
71
87
33
87
80
74
29
68
73
107
94
75
66
70
74
78
65
78
60
32
68
15
85
58
93
106
69
92
101
60
113
139
78
87
60
69
58
Oca
Chloro
Blphenyl
95
108
33
33
30
72
78
90
65
55
59
56
79
67
77
49
32
72
17
36
74
72
104
67
87
82
66
129
165
33
83
60
42
52
4-63
-------
TABLE 4.16 QC SUMMARY (INTERNM.) FOR PCS ANALYSIS
Surrogate Rtcovtry (continued)
SaapU
Facility Matrix
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Fly
8ottoa/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Landfill
Leachate
Leachate
Leacnate
HWell
HWeU
MWell
Well
Pwell
Quench
Quench
Fly
Fly
Fly
Fly
My
BottoeVFly
BottOB/Fly
aottoiYFly
Bottom/Fly
BottoeVFly
BottOB/Fly
Bottoa/Fly
Landfill
Leachate
Leachate
Leachate
Quench
Quench
Quench
Saeple
Otscrlption
Unit 2. 9/28. PN
Unit 2, 9/29, PM
Unit 2. 9/29, PH, Oup
Unit 2. 9/30, AM
Unit 2. 9/30, PN
Unit 2, Coarse
Unit 2. Fine (ESP)
Unit 2, HedluB
Unit 2, 9/28. PH
Unit 2, 9/29, PH
Unit 2. 9/30. AM
Unit 2, 9/30, AM, Oup
Unit 2. 9/30. PH
Perimeter Conpos Itt
North Side
Northtast Corner
Northeast Corner
117
#3
*4
Production Mil
Unit 2. 9/28
Unit 2. 9/30
Unit 1-2. 10/3. AM
Unit 1-2. 10/3, AM. Oup
Unit 1-2. 10/3. PH
Unit 1-2. 10/4, AN
Unit 1-2. 10/4. PN
Unit 1-2. 10/3, AN
Unit 1-2. 10/3. PN
Unit 1-2. 10/3. PN
Unit 1-2. 10/3. PN
Unit 1-2. 10/4. AN
Unit 1-2. 10/4. AN. Oup
Unit 1-2. 10/4, PN
Perimeter Composite
Northeast Corner
Northeast Corner
Southeast Corner
Unit 2. 10/3
Unit 2, 10/3, Oup
Unit 2. 10/4
Saople
Muter
19519
19543
19546
19585
19598
19549
19555
19552
19515
19540
19588
19590
19595
19523
19805-06
19793-94
19817-18
19785-36MSO
19785-86
19785-86W
19759-40
19772-73
19579-80
19509-10
195M-«7
19669
i 19672
19681
19687
19708
19677
19684HSO
196B4NS
19664
19690
t 19693
19712
19600
19623-24
19636-37
19610-11
19649-50
19662-13
19703,27
4-64
4-Chloro-
Blphtnyl
32
98
40
52
112
0.2
11
41
86
51
70
60
10
267
68
59
32
106
63
98
64
58
72
130
62
44
43
14
53
23
40
64
66
61
1
54
59
59
52
48
64
50
SO
42
3,3' .4,1
Tttrachli
Blphtny
42
76
51
64
121
0
9
70
81
75
34
87
21
159
91
109
33
113
103
116
115
102
113
180
85
36
27
7
50
20
94
104
94
90
99
113
87
86
101
90
75
81
102
57
Octa
Chloro
Blphenyl
32
128
96
77
129
32
76
96
100
33
79
37
23
111
82
107
30
105
114
103
97
96
132
170
36
80
.138
97
104
73
102
105
102
39
36
99
78
80
114
95
30
65
92
60
Otca
Chloro
Blphenyl
63
109
34
37
35
74
30
87
87
38
35
79
21
45
38
37
26
31
109
35
77
78
120
107
105
92
156
124
97
75
76
36
36
98
66
66
58
61
93
51
36
62
10S
39
-------
TABLE 4.16 QC SUMMARY (INTERfML) FOR PCB ANALYSIS
Surrogate Recovery (continued)
Sanple
Matrix
Blank
Blank
Blank
Blank
Blank
Blank
Saaple
Description
Laboratory
Laboratory
Laboratory
Laboratory
Laboratory
Laboratory
Sa^lt
Nwber
RM310
RMS76
RB*S78
RBM17
RW633
RM635
4-CJiloro-
Blphenyl
50
42
31
21
59
54
3,3',4,4'
Octa
Tetrachloro Chloro
Biphenyl
61
76
86
93
88
92
Biphenyl
56
90
97
96
99
93
Oeca
Oiloro
Biphenyl
36
34
96
103
33
36
Matrix Spike Results for PCB Analyses
B Leacnate Northeast Corner 19846-47
C MWell 117 19785-66
A Bottom/Fly Unit 1. 9/26. PM 17640
0 Bottom/Fly Unit 1-2, 10/3, PM 19684
MS
45
75
USD
42
78
RPO
2
3
4-65
-------
The Vtrsar laboratory experienced significant difficulties with the
analysts of the first group of samples consisting of 20 fly ash samples.
The problems are summarized in Section 3.4.2 of this report and detailed
in the data appendices. The problems are reflected in poor recoveries of
the lower molecular weight surrogate spikes (4-chlorobiphenyl and
3,3',4,4" tetrachlorobiphenyl) from the fly ash samples collected at
Facilities A and 3. After some adjustments to the procedures for cleanup
of the extracts, recoveries of these surrogate spikes were improved as is
reflected in the recoveries from the fly ash samples collected at
Facilities C and 0. However, the problems with poor recoveries of the
lower molecular weight surrogate spikes recurred in some of the bottom
and combined bottom/fly ash samples analyzed in Group 3. The recoveries
of the higher molecular weight (octachloro and decachloro biphenyls)
surrogate spikes were consistently better than those for the lower
molecular weight surrogate spikes in the fly ash samples. Recoveries
ranged from 15 percent to 135 percent for octachloro biphenyl and
17 percent to 156 percent for decachloro biphenyl.
Recoveries of all surrogate spikes from the field water samples
(analyzed as Group 2) were good; ranges are as follows: 4-chlorobiphenyl,
32 percent to 130 percent; tetrachloro biphenyl, 33 percent to
130 percent; octachloro biphenyl, 30 percent to 139 percent; decachloro
biphenyl, 26 percent to 120 percent.
The Versar laboratory again experienced some problems with recoveries
of the lower molecular1 weight surrogate spikes in the analyses of the
other ash samples (Group 3). The recoveries of 4-chloro biphenyl were
10 percent or less for three samples, and the recoveries of tetrachloro
biphenyl were 10 percent or less for two samples. The poor recoveries
were largely associated with analyses of the coarse and fine fly ash
samples from Facility C. With these exceptions, however, recoveries were
good, with ranges as follows: 4-chloro biphenyl, 11 percent to
267 percent; tetrachloro biphenyl, 21 percent to 159 percent; octachloro
biphenyl, 23 percent to 111 percent; decachloro biphenyl, 21 percent to
4-66
-------
104 percent. The poor recoveries for some QC samples may be related to
the strong attractive force which causes the PCBs to be absorbed onto the
surface of the solid substrates (i.e., fly ash particles).
The recoveries of matrix spikes and matrix spike duplicates using a
SO/SO mixture of native Arochlor 1016 and 1260 as the spikes were
determined on two field water samples. Due to the problems encountered
initially in the analyses of the fly ash samples (Group 1) matrix spikes,
no duplicates were analyzed for the ash samples.
The recoveries on the matrix spikes (MS) and matrix spike duplicates
(MSD), and the relative percent difference (RPD) between the two spikes
were excellent for the liquid samples indicating good precision in the
analyses. The recoveries of the matrix spikes of the ash samples were
51 percent/ 100 percent, and 92 percent.
The analyses of PCB homologs in fly ash samples (Group I), field
water samples (Group 2), and other ash samples (Group 3) overall were in
control, with one exception. The analyses for the lower molecular weight
*
PCB home-logs (tetrachloro biphenyls) in the fly ash samples from
Facilities A and B (analyzed in Group 1) were not in control. The
results of analyses for the lower molecular weight PCB hooologs in these
samples are probably biased toward low values due to poor surrogate spike
recoveries. The results of analyses for the higher molecular weight PCB
homologs (pentachloro biphenyls and more chlorinated) in all samples are
probably as accurate a* current methodology is capable of achieving. The
• «
results of analyses for the lower molecular weight PCB hooologs
(tetrachloro biphenyl and lighter) in all samples except the fly ash
samples from Facilities A and B are accurate for the intended use of the
data.
4.5.1.3 PCDD/PCDFs - Analyses for solid residues, selected field
water samples, and TCLP leachates of selected solid residue samples for
PCDDs and PCDFs were performed by Versar's subcontract laboratory,
Battelle, Columbus. Analyses of each batch of samples for each matrix
4-67
-------
were accompanied by internal QC checks consisting of the following:
analysis of method blanks, determination of recoveries of five
isotopically-labeled PCDO and four isotopically-labeled PCOF internal
standards added to each sample, blank and native spike sample prior to
extraction and analyses, and determination of recoveries of native
PCDD/PCDF spikes in 1 sample per batch (frequency of S percent). The
results of the recovery of the nine isotopically labeled internal
standards are presented in Table 4.17.
Native spike and laboratory method blank samples were processed
during the extraction and cleanup of the samples. The native spike
sample was used to evaluate accuracy, while the laboratory method blank
samples were used to demonstrate the absence of contamination.
The samples were analyzed in three batches. The first batch
consisted of 20 fly ash samples from the four facilities. The second
batch consisted of bottom ash or combined bottom/fly ash from the four
facilities, composites of sample collected from the perimeter of
landfills at Facilities C and 0, and coarse and.fine fractions of a fly
ash sample from Facility C. The third batch consisted of field waters
(field leachate and quench water samples) and leachates prepared in the
laboratory by the TCLP method using selected samples of fly ash and
bottom ash, or combined bottom/fly ash from the four facilities.
In the first batch of 20 fly ash samples, the method blank analyses
were free of PCDD/PCDF contamination, except for trace levels of
hepta-CDD and octa-CDD. The observed levels were less than the desired
detection limit for these congener classes and should, therefore, not
adversely affect the analytical results. Recovery of the analytes from
the native spike sample* ranged from 90 to 110 percent, which is within
the expected range of variation, and within the QC criteria specified in
the Quality Assurance Project Plan (QAPP).
The recoveries of the nine isotopically-labeled internal standards
in fly ash samples were used to correct analytical results for extraction
4-68
-------
TABLE 4.17 QC SIMMRY (INTERNAL) FOR PCOO/PCOF ANALYSIS
Internal Standard (%) Recovery
Facility
A
A
A
A
A
A
A
A
A
A
A
A
A
3
8
a
a
a
a
a
a
a
a
a
a
a
a
a
a
3
Sanple
Matrix
Fly Ash
Fly Ash
Fly Ash
Fly Ash
Fly ASh
Bottom/Fly
Bottom/Fly
Sot torn/Fly
Bottom/Fly
Bottom/Fly
Fly Ash
Quench
Quench
Fly
Fly
Fly
Fly
Fly
Bottom
Bottom
Bottom
Bottom
Bottom
Bottom Ash
Fly Ash
leachatt
Leachate
Leacnate
Quench
Quench
Sample
Description
Unit 1. 9/26. AN
Unit 1. 9/26. AN, Oup
Unit 1. 9/26. PH
Unit 2. 9/26. AN
Unit 2. 9/26, PH
Unit 2. 9/26. AN
Unit 1. 9/26, AN
Unit 2, 9/26, PN
Unit 2. 9/26, AN
Unit 2. 9/26. AN
Lao Leacnate (TCLP)
Unit 2. 9/26
Unit 1. 9/26
Unit 3. 9/28. AN
Unit 3. 9/28. AN, Oup
Unit 4, 9/28, AN
Unit 4. 9/29. P*
Unit 3. 9/29, PN
Unit 4, 9/28, AN
Unit 4, 9/28. AN. Oup
Unit 3, 9/28, AN
Unit 4. 9/29. PN
Unit 3. 9/29, PN
Lab Leacnate (TO?)
Lab Leacnate (TOP)
North Side
Northeast Corner
East Side
Unit 4, 9/28, Oup
Unit 4. 9/28
PCOO/
PCDf TETRA
No.
17629
17632
17638
17644
17647
17620
17624
17635
17620
17620,
17844
17552-5
17542-4
17668
17671
17681
17687
17692
17675
17678
17665
17684
17689
17675
17681
198*5-6
19852-5
19639-4
17532-3
17602-0
-COO
39
92
74
120
34
32
34
89
32
110
94
97
98
83
39
71
85
98
72
92
39
52
92
99
93
33
89
92
70
92
PENTA
-COO
81
80
79
125
61
99
76
100
27
110
110
100
97
55
74
75
75
115
82
82
83
96
88
94
98
37
87 "
102
71
110
HEXA
-COO
57
58
59
85
46
95
71
99
34
93
39
110
100
50
62
58
56
53
74
74
78
94
36
85
100
30
72
95
60
110
HEPTA
-COO
74
76
67
94
44
98
64
98
36
110
86
120
100
50
66
69
43
30
. 72
67
75
91
84
95
110
30
70
100
57
120
OCTA
-COO
76
72
63
93
37
100
61
99
40
120
87
130
110
41
56
77
20
43
65
61
71
96
80
104
120
30
71
109
58
130
TETRA
-CDF
85
94
36
154
85
32
35
99
32
110
94
100
99
95
100
88
38
109
69
37
38
44
91
90
96
31
90
94
70
89
PENTA
-CDF
89
90
86
128
70
90
79
98
31
100
100
110
100
73
37
72
78
109
75
79
79
77
86
90
104
33
90
92
64
100
HEXA
-CDF
15
24
22
5
45
33
66
35
31
100
92
96
100
48
64
61
. 54
11
67
65
69
37
74
91
99
31
74
97
60
110
HEPTA
-CDF
1
2
1
4
3
6
3
3i
Hi
9;
• Ui
Hi
4i
6,
4.
4-
s;
6'
6
5J
3,
r.
*
IK
3J
7(
1*
S'
I2i
4-69
-------
TABLE 4.17 QC SUMMARY (INTERNAL) FOR PCOO/PCDF ANALYSIS
Internal Standard Recovery (continued)
Facility
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Sample
Matrix
Fly
Fly
Fly
Fly
Fly
Bottom/Fly
Bottom/Fly
Bottoo/Fly
Bottom/Fly
Bottom/Fly
Fly
Fly
Landfill
Landfill
Bottom/Fly
Fly Ash
Leachate
Leachate
Leachate
Quench
Quench
Fly
Fly
Fly
Fly
Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Landfill
SottotVFly
Fly Ash
Ltacnate
Leachate
Quench
Quench
Quench
Sample
Description
Unit 2, 9/28, PN
Unit 2. 9/29, PN
Unit 2. 9/29. PN. Oup
Unit 2. 9/30, AN
Unit 2, 9/30, PN
Unit 2, 9/30. PN
Unit 2. 9/30, AH, Oup
Unit 2. 9/28, PN
Unit 2. 9/29, PN
Unit 2. 9/30. AN
Unit 2. coarse
Unit 2. fine (ESP)
Perimeter Composite (M)
Perimeter Composite (N)
Lab Leachate (TCLP)
Lab Leachate (TCLP)
North Side
Northeast Corner
Northwest Corner
Unit 2. 9/30
Unit 2. 9/28
Unit 1-2. 10/3. AN
Unit 1-2. 10/3. AN. Oup
Unit 1-2. 10/3, PN
Unit 1-2. 10/4. AN
Unit 1-2. 10/4. PN
Unit 1-2. 10/4. AN
Unit 1-2, 10/4. PN
Unit 1-2. 10/3. AN
Unit 1-2. 10/3. PN
Perimeter Composite (H)
Lab Leachate (TOP)
Lab Leecnit* (TCLP)
Northeast Comer
Northeast Corner
Unit 2. 10/3. Oup
Unit 2. 10/4
Unit 2. 10/3
POM/
PCOF TETRA
No.
19520
19544
19547
19584
19597
19594
19590
19516
19541
19587
19550
19556
19524
19524
19541
19550
19807-1
19799-0
19819-2
19562-6
19505-0
19668
19671
19680
19686
19707 "
19689
19711
19676
19683
19601
19676
19668
19632-3
19619-2
19657-6
19698-0
19644-4
-COO
90
100
96
35
113
63
78
78
74
35
47
62
110
90
98
100
97
91
83
100
91
95
90
75
93
97
91
88
86
68
83
100
110
94
96
95
111
64
PENTA
-COO
89
79
94
132
78
73
92
80
75
72
57
30
94
62
86
110
110
31
120
130
110
60
74
95
109
101
92
81
83
75
78
120
97
99
89
94
114
63
HEXA
-ax
35
25
50
107
30
75
80
72
73
66
45
18
33
77
76
97
79
55
100
100
78
30
29
77
54
87
77
78
77
70
73
96
100
70
69
78
82
48
HEPTA
-COO
95
132
102
106
113
60
87
66
66
67
29
26
68
67
75
97
76
47
100
100
30
37
83
91
106
101
77
78
80
69
69
92
98
63
59
80
72
44
OCTA
-COO
65
126
57
51
24
56
34
58
67
62
15
20
58
65
82
98
32
43
120
120
76
106
91
101
109
129
80
80
78
61
68
96
100
59
56
84
64
43
TETRA
-CDF
108
101
97
102
119
68
78
71
75
72
38
56
100
35
91
100
39
93
83
94
39
95
95
90
98
94
88
39
35
68
31
100
99
99
100
95
88
68
PENTA
-COF
34
71
95
125
78
75
33
77
73
65
45
30
95
60
89
100
39
73
93
110
95
59
71
99
106
98
91
80
78
71
75
110
110
92
89
39
99
64
HEXA
-CDF
20
14
5
30
7
71
74
54
45
56
48
13
73
63
73
93
31
56
100
96
33
7
17
24
11
31
78
65
70
65
62
100
98
65
68
78
76
49
/
£
£
C
2
e
6
1C
7
il
1C
a
4-70
-------
TABLE 4.17 QC SWHARY (INTERNAL) FOR PCDO/POJF ANALYSIS
Internal Standard Recovery (continued)
Sanple
Facility Matrix
blank
blank
spike
spike
blank
blank
blank
blank
blank
blank
blank
spike
spike
spike
spike
blank
blank
blank
blank
blank
spike
spike
spike
blank
Sample
Description
Laboratory *l
Laboratory 12
Native Laboratory »1
Native Laboratory 12
Method
Method
Method
Method
Method
Method
Method
Native
Native
Native
Native
8lank #1
Blank »2
Blank 13
Blank M
Blank *5
Blank #6
Blank #7
Spike #1
Spike tl
Spike n
Spike M
Method Blank »la
Method Blank *2a
Method Blank «a
Method Blank Ma
Method Blank »5a
Native Spike #la
Native Spike «a
Native Spike »3a
TO? Blank
PCDO/
PCDF TETRA
No. -COO
84
97
95
95
84
90
32
88
76
77
70
66
92
56
74
92
90
93
100
110
88
100
100
75
PENTA
•COO
65
32
72
109
97
100
110
83
81
86
57
70
95
65
91
110
100
100
110
69
100
110
91
80
HEXA
-COO
52
85
49
93
90
78
95
85
75
88
74
67
38
56
91
92
91
99
39
100
35
100
91
63
HEPTA
-COO
54
96
58
102
88
79
39
90
70
81
76
68
98
60
87
92
92
99
37
110
82
110
97
62
OCTA
-030
57
114
62
120
83
31
100
38
74
77
75
69
97
63
88
94
100
94.
91
130
86
120
110
67
TETRA
-CDF
77
102
S3
38
31
91
95
90
73
77
67
65
92
55
51
96
39
91
99
100
39
97
96
66
PENTA
-COF
63
96
72
108
36
32
99
35
69
32
71
65
39
53
79
100
100
95
100
97
91
110
100
69
HEXA
-CDF
47
43
13
30
36
76
95
79
67
32
64
61
30
52
83
92
92
99
36
100
36
100
38
61
4-71
-------
efficiancy and cleanup losses. The expected range of recoveries and QC
criteria for recovery of the internal standards is 60 to 90 percent. The
actual ranges of recoveries for the 20 fly ash samples plus two method
blanks and two native spike samples is summarized below.
RECOVERY RANGE NUMBER OF OUTSIDE QC CRITERIA
INTERNAL STANDARD
Tetra-CDD-13C12
Penta-CDD-13C!2
Hexa-CDD-13Ci2
Hepta-CDD-13C12
Octa-CDD-13Ci2
Tetra-CDF-13Ci2
Penta-CDF-13C]>2
Hexa-CDF-13Ci2
Hepta-CDF-13Ci2
71
32
25
43
20
77
59
5
5
%
- 120
- 132
- 107
- 132
- 129
- 154
- 128
- 80
- 86
Above
12
3
2
11
9
15-
9
0
0
Below
0
2
17
5
9
0
1
21
19
Total
12
10
19
16
17
15
10
21
19
The narrow range of expected recoveries of the internal standards
{60 to 90 percent) is typical of samples with relatively clean matrices
and was not often achievable in the analyses of the fly ash samples.
Because the internal standards are used to correct analytical results for
extraction efficiency and cleanup losses, however, the failure to meet
the QC criteria does not affect the quality of the data provided.
In the second batch of samples consisting of bottom ash, combined
bottom/fly ash, and landfill composite samples, the method blank analyses
were free of PCDD/PCDP contamination except for trace levels of
octa-CDD. The observed levels were less than the desired detection
limits for these congener classes and should, therefore, not adversely
affect the analytical results. Recovery of the analytes from the native
spike samples ranged from 90 to 110 percent, which is within the expected
range of variation, and within the QC criteria specified in the QAPP for
this project.
4-72
-------
As with all analyses, the recoveries of the nine isotopically
labeled internal standards in these samples were used to correct
analytical results for extraction efficiency and cleanup losses. The
expected range of recoveries and QC criteria for recoveries is 60 to
90 percent. The actual ranges of recoveries for the 22 samples in this
batch, plus seven method blanks and four native spike samples is
summarized below.
RECOVERY RANGE NUMBER OF OUTSIDE PC CRITERIA
INTERNAL STANDARD
Tetra-CDD-13C12
Penta-CDD-13Ci2
Hexa-CDD-13C12
Hepta-CDD-13Ci2
Octa-CDD-l3C12
Tetra-CDF-13Ci2
Penta-CDF-l3C12
Hexa-CDF-13Ci2
Hepta-CDF-l3C12
47
30
13
26
15
38
30
13
20
\
- 110
- 110
- 99
- 98 '
- 100
- 100
- 99
- 95
- 94
Above
5
11
5
4
5
6
. 4
1
1
Below
3
3
3
2
5
5
3
5
5
Total
3
14
3
6
10
11
7
6
6
The recoveries of internal standards from the coarse and fine fractions of
fly ash from Facility C were consistently below the QC criteria, as were
the recoveries from native spike 3. The recoveries of internal standards
from the remaining samples were generally within or above the QC criteria.
Because the internal standards are used to correct analytical results for
extraction efficiency and cleanup losses, however, the failure to meet the
QC criteria does not affect the quality of the data provided.
In the third batch of samples consisting of field waters and
laboratory prepared leachates, the method blank analyses were free of
PCDD/PCDF contamination except for trace levels of octa-CDD. The
observed levels were less than the desired detection limits for these
congener classes and should, therefore, not adversely affect the
4-73
-------
analytical results. Recovery of the analytes from the native spike
samples ranged from 90 to 100 percent, which is within the expected range
of variation, and within the QC criteria specified in the QAPP for this
project.
As with all analyses, the recoveries of the nine isotopically
labeled internal standards in these samples were used to correct
analytical results for extraction efficiency and cleanup losses. The
expected range of recoveries is 60 to 90 percent. The actual range of
recoveries for the 26 field waters and laboratory prepared leachates plus
five method blanks, three native spike samples, and one TCLP blank is
summarized below.
RECOVERY RANGE NUMBER OF OUTSIDE QC CRITERIA
INTERNAL STANDARD
Tetra-CDD-13C12-
Penta-CDD-13Ci2
Hexa-CDD-l3C12
Hepta-CDD-13C12
Octa-CDD-l3C12
Tetra-CDF-13CI2
Penta-CDF-13Ci>2
Hexa-CDF-13Ci2
Hepta-CDF-13Ci2
32
27
30
30
30
31
31
31
32
%
- Ill
- 130
- 110
- 120
- 130
- 110
- 110
- 110
- 120
Above
26
25
17
13
19
21
23
13
19
Below
2
2
4
5
7
2
2
4
6
Total
23
27
21
23
26
23
25
22
25
The recoveries of internal standards from most samples were above the QC
criteria rang* indicating better than expected recoveries. The
recoveries froa the leachate prepared from Sample 17620 (bottom/fly ash
from Facility A) and from the field leachate sample (19865-63) from
Facility 8, however, were consistently below the QC criteria. Because
the internal standards are used to correct analytical results for
extraction efficiency and cleanup losses, however, the failure to meet
the QC criteria does not affect the quality of the data provided.
4-74
-------
Overall. the analyses of samples for PCDDs and PCDFs were in control
with very low levels of contamination in blanks, acceptable recoveries of
analytes from native spike samples and generally acceptable to better
than expected recoveries of isotopically labeled internal standards.
These results are consistent with good quality analytical practice. The
data is considered to be acceptable.
4.5.1.4 Organic Constituents - Analyses of selected field water
samples and laboratory-prepared leachates for semi-volatile organic
compounds (Base Neutral/Acid Extractable or BNAs) were performed by the
Versar laboratory. Analyses of each batch of samples of each matrix were
accompanied by internal QC checks consisting of the following analyses:
analysis of laboratory blanks, determination of recoveries of six
surrogate compounds which are readily identified in the GC/MS analysis
and added to each sample before extraction to track the performance of
the extraction and analysis, and determination of the recoveries of
matrix spikes and matrix spike duplicates {the spikes are added to one
sample per batch prior to .extraction and analysis) to monitor the
accuracy and precision of the analysis. The criteria for recovery of
surrogates and the matrix spike and matrix spikt duplicates are specified
in the EPA Contract Laboratory Program and are listed in the summary
tables in this section of this report.
The results of these internal QC checks for the BNA analyses of
samples in this project are summarized in Table 4.18 and discussed below.
No semi-volatile organic compounds were detected in the BNA analyses
of laboratory blanks for the field water samples indicating that the
laboratory water and reagents were free of contamination by this group of
compounds. Diethyl phthalate was detected in the blanks of the EP, TCLP
and MWEP leachates prepared in the laboratory at concentrations from 3 to
24 ug/L. This is a common occurrence resulting from leaching of
phthalates from plastic bottles used in preparation of the leachates.
The blanks did not interfere with subsequent analyses.
4-75
-------
TABLE 4.18 QC SUMMARY (INTERNAL) FOR ORGANIC ANALYSIS
Surrogate Recoveries (%) for Field Water Saaples
Hit;
A
A
B
a
a
a
a
a
a
c
c
c
c
c
c
c
c
c
0
0
0
0
0
0
0
0
0
0
Sanple
i Matrix
Quench
Quench
Quench
Quench
Quench
Quench
Leachate
Leachate
Leachate
Leachate
Leachate
Leachate
NWell
dwell
MWell
Quench
Quench
Quench
Leachate
Leachate
Leachate
Leachate
Quench
Quench
Quench
Quench
Quench
Quench
Blank
Blank
Blank
Blank
Sanple
Description
Unit 1. 9/26
Unit 2. 9/26
Unit 3. 9/28
Unit 3, 9/28, 1/10 Oil
Unit 4. 9/28
Unit 4, 9/28, Quo
East Side
North Side
Northeest Corner
North Side
Northeast Comer
Northwest Corner
»17
«
#4
. Unit 2. 9/30
Unit 2. 9/30
Unit 2. 9/30
Northeast Corner
Northeast Corner
Northeast Corner
Southeast Corner
Unit 2. 10/3
Unit 2. 10/3
Unit 2. 10/3. Oup
Unit 2, 10/3. Oup
Unit 2. 10/4
Unit 2. 10/4
Laboratory
Laboratory
Laboratory
Laboratory
Samle
Niober
17538
17548
17588
17588
17598
17528
19833
19861
19848
19811
19795
19823
19781
19755
19768
19558
19558 MS
19558 MSO
19628
19615
19618RE
19602
19641
1W43RE
196S3
19656RE
19694
19697RE
RB587
R8S87
RB599
RB686
Nitro
Senzene-05
99
87
103
78
97
93
91
90
92
72
103
91
87
101
95
100
99
105
81
28"
55
67
76
64
88
63
68
72
74
88
72
9«
2-Fluoro-
Blphenyl
87
74
96
84
85
94
79
52
72
66
62
81
77
90
86
96
96
103
65
61
59
33
30-
25»
29-
27-
31-
25-
84
90
76
94
Terphenyl
-04
109
as
108
97
90
95
86
46
57
58
38
118
119
131
129
112
111
112
36
8»
23*
22-
14-
26»
19-
30«
9-
0-
101
112
115
108
Phenol
-05
84
36
96"
37
94
96"
35
93
90
68
91
79
32
77
70
77
77
82
37
47
56
69
39
71
104*
83
104*
73
43
72
72
90
2-F1uor
Pneno
94
36
95
95
38
92
75
31
87
73
75
75
34
30
71
92
32
36
28
33
38
63
79
74
91
77
100
69
61
70
76
99
QC Limits
36-114 43-116 33-141 10-94 21-100
Phenol
114
36
113
30
73
34
94
91
34
48
38
83
44
35
72
100
93
97
93
103
103
99
34
18
45
20
35
61
59
69
79
10-123
LEGEND:
MS • iwtrlx spike saiple
HSO • ntrlx spike duplicate saeple
RE • saiple was rtextracted and analyzed
• - value exceeds the QC Halt
4-76
-------
TABLE 4.18 QC SUMMARY (INTERNAL) FOR ORGANIC ANALYSIS
Surrogate Recoveries (%) for Laboratory Leachates (EP. TCLP. and SW-924)
Samp It
Facility Matrix
A
A
A
A
3
a
c
c
0
0
A
A
B
C
0
0
c
0
0
0
0
tot torn/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Fly
Bottom
Bottom/Fly
Fly
Fly
Bottom/Fly
Blank
Blank
Bottom/Fly
Bottom/Fly
Botton
Fly
Fly
Bottom/Fly
Blank
Blank
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
BottOM/Fly
Blank
Leaching
Procedure
EP Toxldty
EP Toxlclty
EP Toxldty
EP Toxlclty
EP Toxldty
EP Toxldty
EP Toxlclty
EP Toxldty
EP Toxldty
EP Toxlclty
HA
NA
TCLP
TCLP
fCLP
Tap
TCLP
Tap
NA
NA
SW-924
SW-924
SW-924
SM-924
SH.924
NA
Staple
Nltro
Nuefcer Benzene-OS
17651
17651MS
17651MSD
176510up
17695
17694
19517
19521
19673
19678
RB701
BUnk
17651
176510up
17694
19521
19673
19678
RB701
Blank
19517
19678*1
19678*2
19678NS
19678MSO
RB712
104
109
107
105
103
104
121*
92
94
98
102
63
111
90
122«
103
107
109
102
108
78
101
93
105
114
89
2-Fluoro-
Blphenyl
94
98
90
95
89
91
108
96
90
94
109
68
87
90
100
84
36
36
109
97
96
82
31
89
92
78
Terphenyl
-04
96
103
98
99
52
57
108
97
70
95
120
60
36
84
84
79
73
32
120
34
66
43
75
83
86
87
Phenol 2-Fluoro- 2
-OS
7«
55
78
76
67
13
10
29
39
51
90
74
34
81
42
12
92
66
90
106*
91
90
85
36
38
Phinol
33
31
34
34
86
3«
57
4«
6'
7*
81
33
18-
SO
5«
2"
61
10«
31
91
83
31
30
31
38
,4,6-Tribronn
Phenol
12
20
71
70
67
5-
15
6«
7«
9«
69
73
21
66
8«
6«
74
18 .
69
67
91
38
91
36
39
QC Lialts
36-114
43-116 33-141 10-94 21-100
10-123
LEGEND:
MS • Mtrlx spike
HSO • Mitrlx splk* duplicate saeple
RE • saeple MU reextracted and reanalyzed
• • value exceeds the QC Unit
4-77
-------
TABLE 4.18 QC SUMMARY (INTERNAL) FOR ORGANIC ANALYSIS
Matrix Spike Results for Field Water Samples (Precision and Accuracy)
SPIKE COMPOUND
Base/Neutral Extractives
1 , 2 . 4-Tr ich lorooenzene
Acenapntnene
2.4-Ofnitro Toluene
Pyrene
N-N 1 troso-0 1 -n-Propy laml ne
1,4-Oichlorobenzene
Acid Extractables
Pentachloropnenol
Phenol
2-Chlorophenol
4-Ch loro- 3-Methy 1 pheno 1
4-Nitropnenol
Facility C
, Quench
Water
Saiple No. 19558
MS
88
86
77
34
88
83
31
77
79
36
23
MSO
91
92
30
38
95
36
33
3*
33
90
18
Matrix Spike
SPIKE COMPOUND
Base/Neutral Extractables
1 . 2. 4-Trich lorooenzene
Acenaphtnene
2,4-OinUro Toluene
Pyrene
N-Nltroso-Oi-n-Propylamine
1 . 4-0 1 ch 1 orobenzene
Acid Extractables
Pentactilorophenol
Phenol
2-Chlorophenol
4-Ch 1 oro-3-nethy I pheno 1
4-Nltroptwnol
EP Toxldty
Facility A.
Sanple No
MS
32
84
90
89
88
80
24
51
43
• 38
as
RPO
3
7
4
5
3
4
2
9
5
5
24
Results
Leachate
Sot ton/Fly
. 17651
MSO
83
83
91
88
89
31
71
72
71
88
98
RPO
1
1
1
1
1
1
101*
34
50"
1
IS
Facility C. Well Water
Saaple No. 19768
MS
90
87
119«
120
84
82
58
72
72
85
78
for Laboratory
SW-924
Facility
Samplt No
MS
77
78
69
76
84
75
36
93
84
34
39
MSO
36
82
107"
116
77
76
57
67
67
76
69
Leachates
Leacnate
RPO
5
6
19
3
7
8
2
7
7
11
10
(Precision
qc
RPO
28
31
38
31
38
23
50
42
40
42
50
Limits (*)
Recovery
39-98
46-113
24-96
26-127
41-116
36-97
9-103
12-39
27-123
23-97
10-80
and Accuracy)
0. 3otton/F1y
. 19678 Dup
MSO
79
79
73
76
90
75
82
91
34
85
78
QC Limits (%)
RPO
3
1
6
0
7
0
5
2
0
1
13
RPO
28
31
38
31
38
28
50
42
40
42
50
Recovery
39-98
46-118
24-96
26-127
41-116
36-97
9-103
12 -8S
27-123
23-97
10-30
LEGEND:
MS • matrix spike saaple
MSO • matrix spike duplicate saeple
RPO • relative percent difference'
• • value exceeds the QC Halt
4-78
-------
The criteria for recovery of surrogate compounds were generally
achieved in the analyses of field water samples and laboratory-prepared
leachates, with some exceptions. The Versar laboratory encountered
difficulties with low recovery of the two heavier base neutral
extractable compounds (2-fluoro biphenyl and terphenyl-04) in analyses of
leachates and quench water from Facility 0. Four samples were
re-extracted and reanalyzed with similar or poorer results indicating
matrix interferences in the extraction and analysis. Problems with low
recoveries were encountered also with the two heavier acid extractable
surrogates (2-fluorophenol and 2,4,6-tribromophenol) in analyses of the
EP and TCLP leachates. Mo acid extractable compounds were detected in
the analyses of samples, however, so this problem is of no consequence.
The criteria for recoveries of Matrix Spike (MS) and Matrix Spike
Duplicates (MSD), and for the Relative Percent Difference (RPD) between
the two were generally achieved. No recoveries below the criteria were
encountered. The precision (RPD) criteria of two of the acid extractable
spikes (pentachlorophenol and 2-chlorophenol) in the analysis of the EP
leachate of bottom/fly ash from Facility A were exceeded.
Overall, the analyses for BNAs in the field water samples and
laboratory-prepared leachates were in control. The data from the
analyses of samples are, therefore, considered valid. Corrective actions
were taken by the laboratory on each occasion of a criteria exceedance in
accordance with the Contract Laboratory Program protocol.
The total organic carbon (IOC) analyses and organic scans w«re also
accompanied by internal quality control checks. These included analyses
of reagent and calibration blanks, analyses of check standards, and
analysis of an EPA quality control sample (WP-1248 for TOO and WP-379 for
organic scan). The blanks were below the detection limits of the
methods. Recoveries in analyses of the check standards and the EPA QC
Standards ranged from 92 to 110 percent, within the QC criteria of 90 to
110 percent specified in the Quality Assurance Project Plan.
4-79
-------
4.5.2 External QA/QC
The external QA/QC samples were field duplicate samples collected at
a frequency of 25 percent. These samples were submitted to the laboratory
as "blind" QC samples (i.e., the analysts were not aware that these
samples were duplicates) to evaluate the precision of the entire sampling
and analysis method. The analytical results of these external QA/QC
samples are presented and evaluated in the following sections.
4.5.2.1 Metals - The results of the field duplicate analyses for
metals and the relative percent differences (RPD) for these duplicate
analyses are presented in Table 4.19. These results are summarized by
sample matrix and facility.
A review of the bottom/fly or bottom ash field duplicate samples
revealed the following. The precision for selenium and cadmium was the
best, while iron, manganese, and zinc had the worst precision. The
precision for Facility A was the best, followed by Facilities 3, C,
and D, sequentially. Finally, although the field duplicates had the
increased variability of sampling, 17 of 44 sample parameter results had
RPDs of <20 percent, which is the RPD criteria for duplicate metals
analyses.
A review of the fly ash field duplicate samples showed the following.
First, the precision for the manganese duplicate analyses was the best,
and the precision for the cadmium duplicate analyses was the worst. The
precision for Facility B was the best, followed.by Facilities A, C,
and 0, sequentially. Finally, the RPD was <20 percent for 41 of 44
analyses. It was expected that the precision of the fly ash field
duplicates would be better than the precision of the bottom/fly or bottom
ash field duplicates because of the more homogeneous nature of the fly
ash samples.
A review of the quench water field duplicate samples showed the
following. First, the RPDs at Facility B were much better than those at
Facility D. This was expected because of the quantity of floating solids
4-30
-------
TABLE 4.19 QC SUMMARY (EXTERNAL) FOR HETALS
TOTAL METALS IN SOLID SAMPLES
'lant
A
A
C
C
0
0
A .
A
3
3
C
C
0
0
B
8
Sample
: M«tr1x
Bottom/Fly
Bottom/Fly
RPO (%)
Bottom/Fly
Bottom/Fly
RPO (%)
Bottom/Fly
Bottom/Fly
RPO (%)
Fly
Fly
RPO (%)
Fly
Fly
RPO (%)
Fly
Fly
RPO (%)
Fly
Fly
RPO (%)
Botto*
Bottoa
Cd
ng/kg
17
15
12.5%
24
27
11.3%
17
18
5.7%
193
186
3.7%
322
316
1.9%
191
157
19.5%
259
172
40.4%
3.8
3.5
Cr
ng/kg
12
16
28.6%
19
26
31.1%
31
36
14.9%
79
66
17.9%
105
98
6.9%
54
52
3.8%
77
67
13.9%
66
78
Cu
ng/kg
369
377
2.1%
3420
608
139.6%
289
728
36.3%
2380
2040
15.4%
745
724
2.9%
531
556
4.6%
516
518
0.4%
792
581
Fe
ng/kg
6650
9140
31.5%
5040
9720
63.4%
8590
95100
166.9%
17400
15000
14.8%
9900
9350
5.7%
8200
8450
3.0%
8320
7190
14.6%
115000
24100
Pb
ng/kg
2200
1140
63.5%
1700
1060
46.4%
571
612
6.9%
5550
5400
• 2.7%
7350
7270
1.1%
3490
3130
10.9%
5450
4600
16.9%
2140
3930
Mn
184
251
30.8%
155
1810
168.4%
3130
640
132.1%
1010
1020
1.0%
895
389
0.7%
388
382
1.6%
857
751
13.2%
1010
938
H1
22
24
8.7%
42
38
10.0%
26
119
128.3%
106
91
. 15.2%
30
76
5.1%
102
95
7.1%
63
55
13.6%
36
90
Zn
ng/kg
1730
3050
55.2%
1570
3250
69.7%
2400
46000
180.2%
15700
14500
7.9%
32700
31800
2.8%
10300
8460
19.6%
22100
18600
17.2%
2350
5760
AS
ng/kg
7.9
12.2
42.3%
5.7
7
20.5%
5.4
6.1
12.2%
41.9
38.0
9.3%
106
89.9
16.4%
16.2
17.7
3.8%
50.7
54.5
7.2%
3.9
6.9
S«
rag/kg
<5
0.0%
<0.5
163.6%
:;
0.0%
<5
«5
0.0%
«!S
0.0%
7.6
5.2
20.3%
9.6
9.1
5.3%
;;•
Hg
nq/kg
6.9
5.0
31.9*
0.62
0.13
110.0*
0.21
0.13
47.1*
27.
23
16.0*
9.3
3.0
15. M
5
4.0
22.2*
1.8
2.0
10.5*
0.12
0.12
RPO (%)
8.2% 16.7% 30.7% 130.7% 59.0% 7.4% 85.7% 84:1% 25.3%
0.0%
0.0*
4-81
-------
TABU 4.19 QC SUWMftY (EXTERNAL) FOR HETALS
TOTAL METALS IN LIQUID SAMPLES
Sample
Plant Matrix
a
8
0
0
Quench
Quench
RPQ (%)
Quench
Quench
RPO (%)
Cd
ug/L
<5.0
-------
TABLE 4.19 QC SUMMARY (EXTERNAL) FOR METALS
Matrix
Plant (Leaciutc)
Fly
(TCLP)
RPO (*)
0 Fly
0 (SW924-CX1)
RPO (%)
0 Fly
0 (SH924-EX2)
RPO (%)
Cd
«Q/L
Cr
«g/L
Cu
mg/L
Ft
mg/L
10.3
8.90
0.487 0.018
0.544 0.0059
12.8
15.0
0.015 0.071 0.0052 <0.005
<0.01 0.114 0.0051 <0.005
100.0% 46.5%
1.9%
0.0%
<0.01 0.116
-------
in the quench water from Facility D. Second, the RPDs for selenium and
mercury analyses were the best, while the RPDs for copper, iron, and zinc
were the worst. Finally, the RPD was <20 percent for 13 of 22 analyses.
A review of the laboratory leachate field duplicate samples revealed
the following. First, the precision of the EF method was good for
cadmium, chromium, manganese, arsenic, selenium, and mercury and was poor
for copper, iron, and lead. The RPD was <20 percent for 13 of the 22 EP
leachate duplicate parameters. Second, the precision for the EP method
was ouch better than for the TCLP and MWEP (SW924) methods. The RPD was
<20 percent for 11 of 22 TCLP duplicate parameters. Finally, for the
MWEP method, only two out of 21 sample parameters which were detected had
an RPO of <20 percent.
Overall, the quality control results for metals based on the
differences between duplicate samples did not suggest the presence of a
significant systematic error. Some random errors are inevitable in a
measurement (sampling and analysis) process. The random anomalies, that
did occur with the metals data were isolated and did not affect
subsequent interpretations of the data.
4.5.2.2 PCBs - The results of the duplicate analyses of selected
samples for individual PCS homologs and total PCBs are summarized by
sample matrix and facility and presented in Table 4.20.
A review of the results for fly ash field duplicate samples revealed
the following. The RPO increased as the level of chlorination
increased. The RPD ranged from 0.0 percent to 4S.5 percent for total
PCBs and from 0.0 percent to 81.0 percent for individual PCS homologs.
A review of the results for the analysis of combined ash and bottom
ash field duplicate samples provided minimal information because no PCBs
were detected in field duplicate samples from Facilities A, B, and C.
However, the RPDs for the combined ash from Facility 0 ranged from
100 percent to 134.7 percent for the individual PCB homologs, and the RPD
4-84
-------
TABLE 4.20 QC SUMMARY (EXTERNAL) FOR PCB ANALYSIS
QC RESULTS FOR SOLIDS
Plant
A
A
A
A
3
8
a
3
C
C
C
C
0
0
0
0
HOMO
Sup It -C8
H«tH« (ng/g)
F1y Ash
Fly Ash
RPO (%)
8otto«/Fly
BottM/Fly
RPO (%)
Fly Ash
Fly Ash
RPO (%)
BottM
Bottom
RPO (%)
Fly Ash
Fly Ash
RPO (%)
Bottoa/Fly
BottostfFly
WO (*)
Fly At*
Fly Ask
W0(»)
Bottc^Fly
BottosVFly
01 TR1 TETRA PENTA TOTAL
-CB -CB -CB -C8 PCB
(ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
0.70 0.70
0.73 0.73
4.2% 4.2%
NO
NO
0.0%
NO
NO
0.0*
NO
NO
0.0*
«0.20 «0.20
0.81 0.81
154.0* 158.0*
NO
NO
0.0*
2.88 2.91 2.41 8.20
2.42 1.72 1.02 5.18
17.4* 51.4* 31.0* 45.5*
<0.20 2.79 -0.20 2.79
1.3S 14.3 18.5 32.15
RPO (*)
172.4* 134.7* 197.8*
168.1*
4-35
-------
TABLE 4.20 QC SUMMARY (EXTERNAL) FOR PCS ANALYSIS
QC RESULTS FOR LIQUIDS
MONO
SaipU -CB
Plant Description ug/L
0 Field Leachate
0 Field Leachate
01
-ca
ug/L
TRI
-CB
ug/L
TETRA
.CB
ug/L
PENTA
-CB
ug/L
TOTAL
PCS
ug/L
NO
NO
RPO (%)
3 Quench Hater 0.002
3 Quencti Meter 0.03
RPO (%)
0 Quench Meter
0 Quench Mater
RPO (%)
175.0*
0.0%
0.002
0.03
175.0%
NO
NO
0.0%
LEGEND:
HOW -C3 - Monochlorlnated Blphenyl
01 -C3 - 01chlorinated Blphenyl
TRI .C8 • THchlorlnated Blpnenyl
TETRA -C8 - Tetrichlorlnated aipheny)
PENTA -CB - PentaehloHnated 31ph«ny1
NO • Not Detected
4-86
-------
for the total PCBs was 168.1 percent. This large RPD nay be attributed
to the heterogeneous nature of the combined ash samples.
A review of results from the analysis field water duplicate samples
showed that for a majority of the duplicates no conclusions of the
precision could be made because of the extremely low concentrations of
PCBs.
4.5.2.3 PCDD/PCDFs - The results of the duplicate analyses for
individual and total PCDD and PCDF homologs is presented in Table 4.21.
These results are summarized by sample matrix and facility.
A review of the fly ash data for PCDD/PCDF field duplicate sample
analyses revealed the following. First, 19 of 24 PCDD and 14 of 20 PCDF
duplicates had an RPD of <20 percent. Second, the precision of the PCDDs
was slightly better than that of the PCDFs. Third, the RFDs increased as
the concentrations of the individual homologs increased. Fourth, the
PCDD precision was best for Facilities C and D, while the PCDF precision
was best for Facilities A and B. Finally, the precision for the
tetra-chlorinated classes of both PCDD and PCDF were best, while the
precision of the hepta-chlorinated classes of both PCDD and PCDF were
worst.
The results from the combined ash and bottom ash field duplicate
sample analyses showed the following. First, 5 of 12 PCDD and 1 of
12 PCDF duplicate results had an RPD of less than 20 percent. This
decreased precision among the combined/bottom ash duplicates is a result
of the heterogeneity of the samples. Second, the precision for the PCDDs
was slightly better than for the PCDFs. Third, the RPOs decreased as the
concentrations of the individual homologs increased. Fourth, both the
PCDD and PCDF precision was better for Facility C than for Facility B.
This may be a result of the Facility C duplicate samples being combined
bottom/fly ash, while the Facility B duplicate samples were exclusively
the more heterogeneous bottom ash. Finally, the precision was best for
the octa-CDD and octa-CDF homologs and was worst for the penta-CDD and
hepta-CDF homologs.
4-87
-------
TABLE 4.21 QC SUMMARY (EXTERNAL) FOR PCDO/PCDf ANALYSIS
QC RESULTS FOR SOLIDS (OIOXIN HOMOLOGS)
Plant
A
A
3
3
B
a
c
c
c
c
0
0
Saaplt
Matrix
Fly Ash
Fly Ash
RPO
Fly Ash
Fly Ash
RPO
Bottom Ash
Bottom Ash
RPO
Fly Ash
Fly Ash
RPO
Bottom/Fly
Bottom/Fly
RPO
Fly Ash
Fly Ash
2,3,7,8
TCDO
"9/9
0.093
0.11
16.7%
0.38
0.38
0.0%
<0.08
0.01
120.0%
1.5
2.1
33.3%
0.62
0.78
22.9%
0.38
0.45
TETRA
.coo
"9/9
2.3
2.8
19.6%
12
11
8.7%
<0.08
0.11
93.3%
31
33
6.3%
14
13
7.4%
5.2
5.1
PENTA
-COO
"9/9
11
14
24.0%
139
114
19.8%
<0.05
0.21
157.4%
710
722
1.7%
47
SO
6.2%
54
46
HEXA
•COO
"9/9
20
20
0.0%
126
123
2.4%
0.07
0.16
78.3%
5565
3946
34.0%
67
78
15.2%
105
103
HEPTA
-COO
"9/9
14
14
0.0%
100
93
7.3%
0.13
0.24
59.5%
1759
3030
53.1%
120
120
0.0%
49
48
OCTA
-COO
"9/9
17
18
5.7%
96
39
7.6%
0.35
0.61
54.2%
2460
3152
24.7%
89
39
0.0%
44
48
TOTAL
-COO
"9/9
64.3
68.3
6.8%
473
430
9.5%
0.55
1.33
83.0%
10525
10883
3.3%
337
350
3.8%
253.2
250.1
•RPO
16.9% 1.9% 16.0% 1.9% 6.5% 8.7% 1.2%
4-88
-------
TABLE 4.21 QC SUMMARY (EXTERNAL) FOR PCDO/PCDF ANALYSIS
QC RESULTS FOR SOLIDS (FURAN HOHOLOGS)
Fac.
A
A
a
a
a
a
c
c
c
c
0
0
Sup It
Matrix
Fly Ash
Fly Ash
RPO
Fly Ash
Fly Ash
RPO
Bottoa Ash
aottM Ash
RPO
Fly Ash
Fly Ash
RPO
Bottom/Fly
Bottom/Fly
RPO
Fly Ash
Fly Ash
2.3,7.3 TETRA
TCOF -OJf
ng/g ng/g
20
23
14.0%
91
97
6.4*
0.05 0.28
0.09 0.68
57.1* 83.3%
164
169
3.0%
2.9 20
3.8 24
26.9% 18.2%
36
36
PENTA
-CDF
ng/g
7.1
10
33.9%
64
65
1.6%
0.18
0.33
58.8%
221
22S
2.2%
20
27
29.8%
32
27
HEXA HEPTA
-COF
ng/g
17
14
19.4%
56
61
3.5%
0.1
0.26
88.9%
336
2353
150.0%
24
35
37.3%
115
21
-OJf
ng/g
14
12
15.4%
40
40
0.0%
0.1
0.26
38.9%
32
77
82.6%
27
36
28.6%
80
3.8
OCTA TOTAL
-CDF
ng/g
2.1
2.3
9.1%
3.1
8.3
2.4%
0.06
0.12
66.7%
60
362
143.1%
6.7
8.4
22.5%
4.9
5.6
-COF'
ng/g
60.2
61.3
1.3%
259.1
271.3
4.6%
0.72
1.65
78.5%
313
3187
118.7%
97.7
130.4
28.7%
267.9
93.4
PCOO *
PCOF
ng/g
124. S
130.1
4.4%
732.1
701.3
4.3%
1.27
2.98
30.5%
11338
14070
21.5%
434.7
480.4
10.0%
521.1
343.5
RPO
0.0% 16.9% 138.2% 181.9% 13.3% 96.6% 41.1%
4-89
-------
TABLE 4.21 QC SUJftARY (EXTERNAL) FOR PCOO/PCOF ANALYSIS
QC RESULTS FOR LIQUIDS (OIOXIN HOHOLOGS)
2.3.7.8 TETRA PENTA HEXA HEPTA OCTA TOTAL
Sup It TOO" -COO -COO -COO -COO -COO -COO
Plant Matrix (ng/1) (ng/1) (ng/1) (ng/1) (ng/1) (nq/1) (ng/1)
0 Field leachate <0.22 0.13 0.4 2.2 8.2 23 33.93
0 Field Leachate <0.26 0.27 <0.22 2.1 3.3 25 36.17
RPO 16.7% 70.0% 113.7% 4.7% 7.1% 3.3% 6.4%
3 Quench Water <0.07 <0.07 <0.03 <0.01 <0.03 0.06 0.06
9 Quench Hater <0.07 <0.07
-------
The results for the field leachate and quench water field duplicate
samples analyses showed the following. First. 9 of 13 PCDO and 10 of
13 PCDF duplicate results had an RPD of less than 20 percent. Second,
the precision was better for the PCDFs than for the PCODs. Third, the
precision was also better for the field leachates than for the quench
water samples, which was expected because the quench water samples
contained floating solids that added to their heterogeneity. However,
these results are misleading because the PCOD and PCDF concentrations
were near the detection limits, which make the RPDs unrepresentatively
high. Finally, the precision was best for the octa-CDD and tetra-CDF
homologs, and was worst for the tetra-CDD and penta-CDF homologs.
Overall, the quality of the PCDD/PCDF data appeared to be excellent
therefore suggesting that the data could be used with a high degree of
confidence.
4.5.2.4 Organic Constituents - The results of the duplicate
analyses for organic constituents are presented in Table 4.22. This
table shows that the precision is generally good. Relative percent
differences were not calculated because of the nature of the analysis and
the multitude of BNA compounds which were tentatively identified.
Therefore, any calculation of RPDs would not be representative of the
actual sampling and analysis precision, due to the nature of the
analytical method.
4-91
-------
TABLE 4.22 QC SUMMARY (EXTERNAL) FOR ORGANICS
Sample
Plant Description
Held Leacha
Fit Id leacha
Ethyl Dimethyl
TOC
(ng/1)
636
567
.0
.0
Organic
Scan
Ong/1)
<0.25
BNA
Peaks
Found
(No.)
22
24
Hexyl
Phthalate
117817
(ug/L)
80
37
Propane
Olol
126307
(ug/L)
110
120
Blphenyl
90437
(ug/L)
51
51
MM
TTHepant
17233715
(ug/L)
82
Thlolane
289167
(ug/D
400
140
Unknown
HCs
(#)
9
10
Unknowns
(#)
8
10
Plant
Saople
Matrix
2-Hydroxy
BNA 2-Methyl 4-Hethyl Benzole Molecular Benzole
Organic Peaks Phenol phenol phenol Acid Sulfur Thlolane Acid
TQC Scan Found 108952 95487 106445 65850 10544500 289167 69727
(•B/l) (ms/1) (Ho.) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L)
B Quench Water 421.0 «0.25 20 380 40 92 2100 29
3 Quench Mater 416.5 <0.25 20 380 44. 94 2100 130
23
SO
42
Plant
Hexanoic
Add
Sample 142621 Unknowns
Matrix (ug/L) (»)
8 Quench Water 58 13
a Quench Water 37 12
Plant
0
0
Sanple
Matrix
Methyl
BNA 2-Hethyl 4-Methyl Benzole Hexyl Hexanoic Pentanolc
Organic Peaks Phenol phenol phenol Acid Phthalate Add Add
TOC Scan Found 108952 95487 106445 65850 117817 142621 646071
(mg/1) (av/1) (No.) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L)
Quench Water 165.0
Quench Water 153.0
«0.25
25
25
60
71
23
570
900
45
51
17
34
Samle
Methyl Furan Benzene Tetra Methyl
Benz- Pentane- Carbox- Propanotc Oeeanoic Purlne
aldehyde dlol aldehyde Acid Add done Unknown Unktmn
100527 144194 67470 501520 544638 58082 Org Acids HCs Unknowns
Plant Matrix (ug/L) (ug/L) (ug/L) (ug/L) (ug/L) (ug/L)
(#)
(*)
0 Quench Water
0 Quench Water
22
17
23
12
4-92
23
22
9
17
-------
5.0 EVALUATION
In this section, the data presented and discussed in Section 4.0 are
summarized and evaluated. To facilitate this evaluation, the data were
averaged by facility, sample type, and analytical parameter
combinations. Then, the data were evaluated with respect to previously
reported information, variations between sample types, variations between
laboratory leachate preparation procedures, municipal waste combustor
(MWC) facility design and operation, and characterization of the residues
as hazardous wastes. Section 5.1 presents the concentration ranges for
each sample type and analytical parameter from this study and compares
them to the concentration ranges from previous studies. Section 5.2
presents the data summary tables and an evaluation of the significant
trends observed from these tables. Section 5.3 provides a qualitative
evaluation of the relationships between MWC facility design and operating
characteristics and the concentrations of constituents in the residues.
Finally, Section 5.4 presents an overall assessment of the hazardous
waste characteristics of the MWC residues based on existing standards and
criteria.
. 5.1 Comparative Evaluation With Previously Reported Information
The data extracted from the documents identified in the literature
review (see Section 2.0) were summarized by sample type and analytical
parameter. From the summarized data, a concentration range was
determined for each sample type/analytical parameter combination from the
previous studies. The lower end of any given range was the miriimum
concentration reported in any previous study for that particular sample
type/analytical parameter combination. Similarly, the upper end of any
given rang* was the maximum concentration reported in any previous study
for that particular sample type/analytical parameter combination. Using
an analagous approach, the concentration range was determined for each
sample type/analytical parameter combination from this study. However,
previous studies did not provide any data for PCDD/PCDFs or organic
constituents (i.e., BNAs) in laboratory-prepared leachates,-or
5-1
-------
for PCBs or PCDD/PCDFs in field water samples (i.e., quench water, field
leachate, and ground water). Sections 5.1.1 through 5.1.3 present the
concentration ranges from this study and from previous studies for the
available sample type/analytical parameter combinations and provide a
narrative evaluation of the findings.
5.1.1 Solid Samples
The concentration ranges for metals in fly ash and combined ash are
presented in Table 5.1. As can be seen from this table, the results for
the fly ash from this study are within the concentration ranges from
previous studies for all metals except copper, mercury, and selenium,
where Versar's results are slightly higher. Similarly, for the combined
ash,-the results from this study are within the concentration ranges from
previous studies for all metals except copper and zinc. One possible
explanation for these discrepancies may be that in several of the previous
studies, only one MWC facility was sampled, and the concentration range
arising from the sampling, analytical/ and operational variability at one
facility would not be expected to encompass the concentration range
resulting from four different facilities. Generally, the results for
both the fly ash and combined ash from this study extend fcom the low and
to the midpoint of the range from the previous studies.
The concentration ranges for PCBs in fly ash and combined ash are
presented in Table 5.2. Both the fly ash and combined ash results from
this study are within the concentration ranges from previous studies for
every individual PCS homolog, as well as for total PCBs. Generally, the
results from this study are near the lower end of the ranges from the
previous studies for both ash types. One noteworthy trend is that the
higher chlorinated species of PCBs (i.e.. the hepta- through deca-
chlorinated species) were not detected either in this study or in the
previous studies, except for negligible concentrations of hepta-CB and
octa-CB in the fly ash.
5-2
-------
TA8U 5.1 COMPARATIVE EVALUATION OF TOTAL METALS IN SOLID SAMPLES
FLY ASH
fetal
Arsenic (As)
Caoftlua (Cd)
Chronlua (Cr)
Copptr (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (-Kg)
Nickel (HI)
Seleniun (Se)
Zinc (In)
Concentration Rang* Fro*
This Study (ng/kg)
16 • 149
107 - 475
48 - 105
484 . 2.380
5,960 • 22.300
2,830 - 14,400
320 - 1,410
0.94 - 35.0
52 • 245
N0(5) - 15.6
8,460 - 38,800
Concentration Rang* Fro*
Previous Studies (ng/kg).
References
4.3 - 750
5.0 - 2,210
21 - 1,900
187 • 2.300
900 - 37,000
200 - 26,600 •
171 - 3.500
N0(0.02) - 6.77
N0(1.5) . 3.600
N0(0.2) - 12
2.800 - 152.000
42, 53
34, 42
34, 53
53
34, 53
30. 42. 53
34, 53
30, 53
46
30
30, 42. 53
COMBINED ASH [2]
Metal
Arsenic (As)
Cadniua (Cd)
Chroalue) (Cr)
Cdpper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (N1)
Selentue (Se)
Zinc (In)
Concentration Range Fro*
This Study (ng/kg)
2.2 - 24.6
1.1 - 45.0
12 - 332
193 - 10,700
2.100 - 115.000
259 • 13,200
110 - 3.130
0.11 • 8.7
13 - 556
NO(O.S) • 1.4
54S - 46,000
Concentration Rang* Fro*
Previous Studies (mg/kg)
References [1]
0.8
0.18
13
40
690
31
14
N0(0.02)
W(l.S)
W(0.2)
92
50
100
1.500
3,400
133.500
36.600
4.800
17.5
12.910
50
7,000
53
53
30, 42. 53
53
53
53
46, 53
30, 53
46, S3
53
46, 53
W - Not detected: tht detection Halt is given in parentheses following NO.
[1] • The niaBer(s) in the reference coluen corresponds to the reference iteai nuefcer in Appendix A from
which the conctntratlon range froB previous studies was extracted.
[2] - The concentration ranges were derived froai both combined bottoaVfly and discrete bottoe) ash sanples.
5-3
-------
TABLE 5.2 COMPARATIVE EVALUATION OF PCBs IN SOLID SAMPLES
FLY ASH
PCS How log
Mono-CB
01 -CB
Tr1-CB
Tetra-CB
Penta-C8
Hexa-CB
Htpta-CB
Octa-CB
Nona-CB
Dtca-C8
TOTAL PCBs
PCS Homo log
Conctntratlon Rang* Fnm
This Study (ng/g)
NO(O.l) • 1.46
NO(O.l) - 7.37
NO(O.l) - 7.67
NO(O.l) - 5.52
NO(O.l) - 2.25
NO(O.l)
NO(O.l)
NO(O.l)
NO(O.l)
NO(O.l)
NO(O.l) - 24.8
COMBINED ASH [2]
Conctntratlon ftangt From
This Study (ng/g)
NO(O.l)
NO(O.l) - 1.35
NO(O.l) - 14.3
NO(O.l) • 16.5
NO(O.l)
NO(O.l)
Itt(O.l)
NO(O.l)
NO(O.l)
NO(O.l)
NO(O.l) - 32.2
i 1 1a1t Is givtn tn partnthtw
Conctntration ftangt Fro»
Previous Studies (ng/g)
NO(O.Ol) - 9.7
NO(O.l) - 10
NO(O.l) - 25
0.5 - 470
NQ(O.l) - 130
NO(O.l) - 55
NO(O.Ol) • 0.2
NO(O.Ol) • 2.5
NO(O.Ol)
NO(O.Ol)
NO(O.l) - 250
Conctntration Rangt Fro*
Prtvlous Stud Its (ng/g)
NO(O.Ol) - 1.4
NO(O.l) - 5.5
NO(O.l) • 30
NO(O.l) . 47
HO(O.l) - 48
NO(O.l) - 39
NO(O.Ol)
NO(O.Ol)
NO(O.l)
NO(O.l)
NO(O.l) - 180
is following NO.
k i tmfmvmnrm i +•• n i^Mf» i n
References [I]
35. 76
35, 76
76
35. 76
35. 76
35. 76
35, 76
35, 76
35
35
30. 35. 76
References [1]
35, 76
35, 76
35. 76
35. 76
35. 76
35, 76
76
76
35
35
30, 76
iltMArfl* A frM
Mono-CB
01-CB
TM-CB
Tttra-CB
Penta-CB
Hexa-CB
Htpta-CB
Octa-CB
Nona-CB
Dtca-CB
TOTAL PCBS
NO - Not Otttcttd: tht dttt«
[1] - Tht nu0btr(s) In tht n
which tht conctntratlon rangt froa prtvlous studies MU extracted.
[2] - Tht conctntratlon rangt* wtrt derived froa both coetolntd bottpi/fly and discrete botton ash sanples.
5-4
-------
The concentration ranges for PCDDs and PCOFs in fly ash and combined
ash are presented in Table 5.3. This table shows that both the fly ash
and combined ash results for PCDDs and PCOFs generally exceed the
'concentration ranges from the previous studies, particularly for the
highly chlorinated species of both PCDDs and PCDFs (i.e., the hexa-
through octa-chlorinated species of both PCDDs and PCDFs). These
exceedances are more pronounced for the PCDDs than for the PCDFs.
Similarly, they are more pronounced for the fly ash than for the combined
ash. These discrepancies may again be explained by the lack of a
complete data base from previous studies.
5.1.2 Laboratory Leachates
Table 5.4 presents the concentration ranges for metals in the EF
(extraction procedure toxicity) leachates prepared from fly ash and
combined ash samples. The results for the EP-prepartd fly ash leachates
from this study are within the concentration ranges from previous
studies, except for iron and manganese, where slightly higher results
were found by Ve-rsar. Similarly, the results for. the EP-prepared
combined ash leachates from this study are within the concentration
ranges from previous studies for all metals except copper, iron, lead,
and zinc. As was the case for the solid samples, these slight
discrepancies may be attributed to the concentration ranges which were
extracted from one previous study of only one MWC facility.
The concentration ranges for metals in the TCLP (toxicity charac-
teristic leaching procedure) leachates prepared from fly ash and combined
ash samples are given in Table 5.5. Although the cadmium, copper, lead,
and nickel results £torn the Versar study are within the concentration
ranges from the previous studies, the results for the TCLP-prepared fly
ash leachates from this study are generally higher than the upper end of
the ranges from the previous studies. Similarly, the results for the
TCLP-prepared combined ash leachates from this study exceeded the upper
end of the ranges from previous studies for cadmium, chromium, manganese.
5-5
-------
TABLE 5.3 COMPARATIVE EVALUATION OF PCOO/PCOFs IN SOLID SAMPLES
FLY ASH
Conetntratlon
PCOO/PCOF Homo log
2,3.7.8-TCDO
Tetra-CDO
Penta-COO
Hexa-CDO
Htpta-COO
Octa-COO
TOTAL PCOOs
2.3.7.8-TCOF
Tetra-COF
Penta-COF
Htxa-COF
Htpta-COF.
Octa-COF
This Study
0.
2
64
11 -
.3 -
a -
18 -
14 -
11 -
.3 -
Rangt Fro»
(ng/g)
3.9
43
722
5.565
3,030
3,152
10.883
It.A.
7
3
1
20 -
.1 -
14 -
.8 -
.4 -
169
226
2.353
666 .
362
Conetntratlon
Prtvlous
N0(0
Rangt Fro»
Studies (ng/g)
.
2
1) -
.4 -
0.5 -
N0(0
N0(0
N0(0
N0(0
0
•
•
•
•
.2 -
1) -
1) -
1) -
1) -
0.4 -
N0(0.
. ND(0.
N0(0
N0(0
*
•
1) -
1) -
1) -
1) -
42
250
650
2.496
410
341.5
4,700
5.4
460
1,800
1,100
500
255
References
30
35
12
12
12. 30
35
35
12
76
f
,
76
»
»
76
f
*
76
76
,
76
76
76
76
35.
76
76
76
[13
76
TOTAL PCOFs
60.2 - 3,187
NO(O.l) - 3,000
30. 76
TOTAL PCOO/PCOFs
124.5 - 14.070
NO(O.l) - 7,700
12. 30, 35, 76
COMBINED ASH [2]
I «
PCOO/PCOF Homo log
2.3.7,8-TCOO
Tttra-COO
Ptnta-COO
Htxa-COO
Htpta-COO
Octa-COO
Conetntratlon Rangt Fro»
This Study (ng/g)
NO(O.l) - 0.78
NO(O.l) - 14
NO(O.l) - 50
NO(O.l) - 78
NO(O.l) - 120
0.16 - 89
Conetntratlon Rangt Frot
Prtvlous Studies (ng/g)
0.2 - 6.7
0.13 - 92
NO(O.l) - 13
NO(O.l) - 9.0
NO(O.l) - 1.7
NO(O.l)
References [1]
76
76
35. 76
35. 76
35. 76
35. 76
TOTAL PCOOS
0.27 - 350
NO(O.l) - 110
30. 35, 76
5-6
-------
TABLE S.3 (CONTINUED)
COMBINED ASH [2]
Concentration Range Fro» Concentration Range Fnm
PCDO/PCOF Homolog This Study (ng/g) Previous Studies (ng/g) References [1]
2.3.7.8-TCDF ND(O.l) - 12 0.2 - 1.3 76
Tetra-COF NO(O.l) - 91 NO(O.l) - 8.4 76
Penta-COF NO(O.l) - 37 NO(O.l) - 12 76
Hexa-COF NO(O.l) - 35 NO(O.l) - 2.5 35, 76
Hepta-COF NO(O.l) - 36 NO(O.l) - 0.8 35, 76
Octa-COF NO(O.l) - 8.4 NO(O.l) - 0.9 35. 76
TOTAL PCOFs 0.18 - 153.9 NO(O.l) - 65 30, 35, 76
TOTAL PCOO/PCOFs 0.48 - 480.4 NO(O.l) - 175 30, 35, 76
N.A.- Not Available
NO • Not Detected; tne detection Halt Is given In parentheses following NO.
[1] - The nui*er(s) In the reference column corresponds to the reference Item number in Appendix A from
which the concentration range from previous studies wes extracted.
[2] • The concentration ranges were derived from botn combined bottom/fly and discrete bottom ash samples.
5-7
-------
TABLE S.4 COMPARATIVE EVALUATION OF METALS IN EP LEACHATES
FLY ASH
Metal
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (N1)
Selenium (Se)
Zinc (Zn)
Metal
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (N1)
Selenium (Se)
Zinc (Zn)
Concentration Range From
This Study (mg/L)
NO(O.Ol)
6.02 - 18.0
NO(O.OOS) - 0.038
0.041 - 1.62
N0(0.005) - 0.49
4.72 - 25.2
2.71 - 8.03
MO (0.008)
0.137 - 1.92
NO(O.OS)
188 - 728
COMBINED ASH [2]
Concentration Range From
This Study (rag/L)
NO(O.Ol)
0.06 . 0.827
0.0059 - 0.150
0.039 • 1.19
4.S • 143
2.09 - 34
3.60 • 5.24
N0(0.008)
0.241 . 0.415
N0(0.05)
38.5 - 726
Concentration Range From
Previous Studies (ng/L)
NO(O.OOl) - 0.858
0.025 . 100
0.006 - 0.135
0.033 - 10.5
0.189 - 0.202
0.019 • 53.35
0.005 - 5.79
N0(0.0002) • 0.007
0.09 . 2.90
H0( 0.002) - 0.085
3.36 • 768
Concentration Range From
Previous Studies (ng/L)
NO(O.OOl) .0,122
0.018 - 3.94
K0(0.007) - 0.46
0.713 - 0.898
94.3 - 96.5
0.02 - 21.0
5.62 - 6.21
N0(0.0002) - 6.00
0.463 - 2.03
N0(0.002) • 0.10
64.5 - 81
References [1]
30. 53
42. S3
30. 53
53
53
30, 53
53
30, 53
53
30, 53
53
References [1]
30, 53
30, 53
30, 53
53
53
53
53
30. 53
53
30. 53
53
NO ' Not Detected; the detection limit Is given In parentheses following NO.
[1] ' The numbers) in the reference column corresponds to the reference item number 1n Appendix A from
which the concentration range from previous studies MS extracted.
[2] ' The concentration ranges were derived from both combined bottom/fly and discrete bottom ash samples.
5-8
-------
TABLE 5.5 COMPARATIVE EVALUATION OF HETALS IN TOP LEACHATES
FLY ASH
Metal
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (N1)
Selenium (S«)
Zinc (Zn)
Concentration Range Fr
This Study (ng/L)
NO(O.Ol) - 0.111
0.015 - 17.2
NO(0.005) - 0.544
NO(O.OOS) - 0.201
NO(O.OOS) - 190
NO(O.OS) - 15.2
0.049 - 14.7
NO(O.OOS)
N0(0.015) - 1.52
NO(O.OOS)
0.151 • 746
Concentration Range From
Previous Studies (ng/L)
References [1]
N.A.
0.03 • 20.3
0.02 • 0.12
0.02 - 14.7
0.03 - 0.17
5.3 • 36.6
0.01 > 7.19
N.A.
0.09 - 2.48
N.A.
•2.27 - 8.85
N/A
S3
S3
53
53
S3
S3
N/A
S3
N/A
53
COMBINED ASH [2]
Metal
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (Nl)
Selenium (Se)
Zinc (Zn)
Concentration Range From
This Study (ng/L)
NO(O.Ol) - 0.037
0.025 • 3.32
NO(O.OOS) • 0.439
NO(O.OOS) - 0.019
0.828 - 60.6
0.655 - 30.1
4.2 • 11.9
N0(0.008)
0.344 - 0.805
NO(O.OOi)
23.3 • 373
Concentration Range From
Previous Studies (ng/L)
0.01
0.01
0.01
0.02
2.18
0.05
3.22
N0(0.0002)
0.09
0.01
23.5
- 0.1
. 1.9
- 0.32
- 0.09
- 230
• 47
- 7.47
• 0.10
. 0.41
. 0.05
- 83.2
References [1]
53
S3
S3
53
S3
S3
S3
S3
53
S3
53
N.A.- Not Available; N/A - Not Applicable
NO - Not Detected: the detection limit Is given In parentheses following NO.
[1] - The numoer(s) In the reference column corresponds to the reference Item number In Appendix A from
which the concentration range from previous studies MM extracted.
[2] - The concentration ranges were derived from both combined bottom/fly and discrete bottom ash samples.
5-9
-------
nickel, and zinc. Again, these discrepancies may have been a result of
the limited amount of-data available in previous studies.
The concentration ranges for metals in deionized water leachates
prepared from the fly ash and combined ash are presented in Table 5.6.
Special care should be taken when comparing and evaluating the data in
this table because the monofilled waste extraction procedure (MWEP;
SW-924) was used by Versar, but the nature of the deionized water
leaching procedure used in the previous study is not known.
Nevertheless, Table 5.6 shows that the concentrations from this study for
both the fly ash and combined ash are comparable to the concentrations
from previous studies.
5.1.3 Field Water Samples
The concentration ranges for metals in field leachate and quench
water samples are presented in Table 5.7. The field leachate results
from this study are within the concentration ranges from the previous
studies .for every metal. Generally, the concentrations from this study
•are in the lower end of the concentration ranges from previous studies.
Conversely, the quench water concentrations from this study exceed the
upper boundary of the ranges from previous studies for metals. One
possible explanation for this is that several of the quench water samples
from this study contained appreciable amount of solids (i.e., ash
material). Since total metals were quantified, the samples were
subjected to the acid digestion and subsequent analysis without a
filtration step. AM a result, the quench water sample results may have
been biased high in comparison to other studies by the solid materials.
Nevertheless, the data reported in this study characterizes the quality
of the waatewater which is discharged.
Table 5.8 presents the concentration ranges for organic constituents
(BNAs) in field leachate and quench water samples. Both the field
leachate and quench water results from this study are generally within
the concentration ranges from the previous studies, where the data are
5-10
-------
TABLE 5.6 COMPARATIVE EVALUATION OF METALS IN OEIONIZEO WATER LEAOATES
FLY ASH
Metal
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Hercury (Hg)
Nickel (141)
Selenium (Se)
Zinc (Zn)
Concentration Range From
This Study (ng/L)
NO(O.Ol)
NO(O.Ol) . 0.122
NO(O.OOS) • 0.15
NO(O.OOS) - 0.089
NO(O.OOS) - 0.167
NO(O.OS) - 0.148
NO(O.OOl) . 0.0052
N0(0.02)
NO(O.OIS) - 0.022
NO(O.OOS) - 0.108
HO (0.003) . 1.22
COMBINED ASH [2]
Concentration Range From
Previous Studies (ng/L)
N.A.
0.03 - 0.17
0.04 . 0.08
N0(0.02)
N0(0.03)
0.26 - 35.0
NO(O.Ol)
N.A.
NO(O.OIS) - 0.09
. N.A.
0.67 - 4.15
References [1]
N/A
53
53
53
53
53
53
N/A
53
N/A
53
Metal
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (N1)
Selenium (Se)
Zinc (Zn)
Concentration Range From
This Study (mg/L)
NO(O.Ol)
NO(O.Ol)
NO(O.OOS)
NO(O.OOS) - 0.07
NO(O.OOS) - 0.038
NO(O.OS) • 0.063
NO(O.OOl) - 0.0021
N0(0.02)
NO(O.OIS)
NO(O.OOS)
N0(0.003) - 0.067
Concentration Range From
Previous Studies (ng/L)
References [1]
NO(O.OS)
0.01 - 0.03
NO(O.Ol) . 0.02
0.11 - 0.19
N0(0.03)
ND(O.OS) - 2.98
NO(O.Ol)
NO(O.IO)
N0(0.02) - 0.09
NO(O.OS)
0.38 - 0.96
53
53
53
53
53
53
53
53
S3
53
53
N.A.- Not Available; N/A - Not Applicable
NO • Not Detected; tiw detection limit Is given In parentheses following NO.
[1] - The number(s) In the reference column correspond! to tne reference item matter In Appendix A fro*
which the concentration rang* from previous studies MM extracted.
[2] - The concentration ranges were derived from both combined bottom/fly and discrete bottom ash samples.
5-11
-------
TABLE 5.7 COMPARATIVE EVALUATION OF TOTAL NETALS IN FIELD WATER SAMPLES
FIELD LEACHATE
Metal
Arstnlc (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Nn)
Mercury (Hg)
Nickel (N1)
Seleniua (S«)
Zinc (Zn)
Concentration Range Froai
This Study («g/L)
NO(O.Ol)
NO(O.OOS)
NO(O.QOS)
0.045
0.758
NO(O.OS)
0.103
N0(0.0002)
NO(O.OIS)
NO(O.OOS)
0.048
- 0.218
• 0.044
• 0.914
- 2.57
- 121
- 2.32
• 4.57
• 0.008
- 0.412
• 0.037
• 3.30
Concentration Range Fro*
Previous Studies (ng/L)
References [1]
NO(O.OS)
NO(O.Ol)
N0(0.006)
N0(0.006)
«( 0.007)
NO(O.OOl)
N0( 0.002)
N0(0.002)
NO(O.OS)
N0(0
NO(O.Ol)
- 70.2
- 17.0
- 33.4
- 24.0
- 5,500
- 14.2
- 1,400
- 0.064
- 7.5
.01)
• 1,000
30. 52
30, 52
30, 52. 69
30. 52
30, 52, 69
52
52
30, 52
30. 52
30
30, 52
QUENCH HATER
Metal
Concentration-Range Fro*
This Study (rag/L)
Arsenic (A$)
Cadmium (Cd)
Chrc«1u») (Cr)
Cooper (Cu)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (Ni)
Selenium (Se)
Zinc (Zn)
NO(O.Ol)
NO(O.OOS)
0.0085
0.02
0.037
0.178
0.024
N0(0.0002)
0.009
0.542
1.91
1.12
13.1
141
37.9
12.6
0.022
0.849
10(0.0125)
0.087 . 192
Concentration Range From
Previous Studies (mg/L)
References-[1]
NO(O.OOl) .
110(0.004} •
10(0.007) •
N0(0,
N0(0.
NO(O.OOl) •
N0(0.
N0(0.0002) •
N0(0,
(€(0.002) .
N0(0
0.0031
0.067
> 0.014
006)
007)
0.688
002)
• 0.0089
015)
> 0.036
002)
46, 56
46. 56
46, 56
46
46
46, 56
46
46, 56
46
46. 56
46
NO - Not Detected: the detection llartt ts given (a parentheses following NO.
[1] - The nueoer
-------
TABLE 5.3 COMPARATIVE EVALUATION OF BNAs IN FIELD MATER SAMPLES
FIELD LEACHATE
SKA Conpound
Biphtnyl
01-n-butyl phthalata
01ethyl phthalate
Dimethyl phthalate
Dimethyl propanedlol
Bis 2-ethylhexyl phthaiate
Naphtha lent
Phenol
Thlolant
SNA Compound
Acenaphthylene
Benzole add
01-n-butyl phthai ate
Bis 2-ethylhexyl phthaiate
Fluoranthene
Hexanolc add
2-Hydroxybenzolc acid
Methylpentanolc add
2-Methyl phenol
4-Metnyl phenol
Naphthalene
Phenanthrene
Phenol
Pyrene
Concentration Range Fro*
This Study (ug/L)
NO(N.A.) - 51
N0(2.5)
N0(22)
NOU.6)
NO(N.A.) . 120
N0(2.5) - 80
N0(1.6)
NO(l.S)
NO(N.A.) - 400
QUENCH MATER
Concentration Range Froai
This Study (ug/L)
110(3.5) - 6.0
NO(N.A.) - 3,800
N0(2.5) • 3.0
N0(2.5) - 8.0
N0(2.2) • 6.0
NO(N.A.) . 920
NO(N.A.) - 50
NO(N.A.) . 88
N0(2.7) - 86
N0(2.7) - 94
NOU.6) . 8.0
N0(5.4) . 6.0
NO(l.S) - 640
N0(1.9) - 5.0
Concentration Rang* Fron
Previous Studies (ug/L)
N.A.
N0(2.5) - 150
N0(2.2) - 300
N0(1.6) - 55
N.A.
N0(2.5) - 150
N0(1.6) - 19
N0(1.5) - 29,800
N.A.
Concentration Range Fro*
Previous Studies (ug/L)
0.46 - 28
N.A.
N0(0.6) - 13
N0(0.6) - 1.3
0.45 • 1.5
N.A.
N.A.
N.A.
N.A.
N.A.
N0(0.6) - 3.0
N0(0.6) • 5.0
N.A.
0.57 - 4.4
References [1]
N/A
52
52
52
N/A
52
52
52
N/A
References [1]
35
N/A
35
35
35
N/A
N/A
N/A
N/A
N/A
35
35
N/A
35
N.A.. Not Available; N/A - Not Applicable
NO - Not Detected: the detection Malt is given in parentheses following NO.
[1] - The nunber(s) In the reference coluen corresponds to the reference Itea
which the concentration range fro* previous studies MU extracted.
In Appendix A fro»
5-13
-------
available. The results of both this study and the previous studies
indicate that the polycyclic aromatic hydrocarbons (e.g., acenaphthylene,
fluoranthene, naphthalene, phenanthrene, and pyrene), the phthalate
esters (e.g.. bis-2-ethylhexyl phthalate, di-n-butyl phtnalate, diethyl
phthalate, and dimethyl phthalate), and the phenols (e.g., phenol, methyl
phenol, and dimethyl phenol) are the predominant SNA compounds that were
detected in the field water samples.
5.2 Significant Trends in the Data from this Study
The data generated from the samples collected in this study were
summarized by facility and sample type (e.g., ground water, field
leachate, fly ash, combined ash EP leachate, etc.) to facilitate data
evaluation. The data summaries were generated by averaging the
individual analytical results for each sample type from each facility.
One summary was prepared for the metals data, and another one was
prepared for the PCBs, PCOOs, and PCDFs. A summary was not prepared for
the BNAs because very few of the individual SNA constituents were
detected often enough to allow for a meaningful comparative evaluation.
5.2.1 Metals
The summary of the metals data is presented in Table 5.9. The
metals data for the solid samples showed that the fly ash contained more
total metals than the combined (i.e., bottom/fly) ash or the bottom ash.
The fly ash consistently exhibited higher concentrations o£ cadmium,
chromium, lead, nickel, zinc, arsenic, mercury, and selenium than the
combined ash or bottoo ash. However, the combined ash and bottom ash
contained higher concentration* of copper and iron. The fly ash
contained approximately the same, amount of manganese as the combined ash
and bottom ash. These observations suggest that the which tend to become
more concentrated in the fly ash are the more volatile metals, while
those metals that are more highly concentrated in the combined ash and
bottom are the higher boiling point less volatile metals.
5-14
-------
TABLE 5.9 SUMMARY RESULTS FOR METALS
FACILITY A
Sanplt
Typt
Fly Ash
Fly Ash
Fly Ash
Fly Ash
Fly Ash
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Bottom/Fly
Samp It
Matrix
Solid
EP Tox.
TCLP
SW924-EX1
SW924-EX2
Solid
EP Tox.
TCLP
SW924-EX1
SW924.EX2
units
mg/kg
«g/L
mg/L
mg/L
mg/L
mg/kg
mg/L
mg/L
mg/L
mg/L
Cd
190.8
6.37
0.023
<0.015
<0.01
19.3
0.827
0.682
<0.01
<0.01
Cr
70.3-
<0.005
0.136
0.01
<0.005
16.3
0.016
0.096
<0.005
<0.005
Cu
1716
0.15
<0.005
0.058
0.009
356
1.19
0.019
<0.005
<0.005
Ft
15646
<0.005
190
0.167
0.057
5904
4.50
60.6
<0.005
<0.005
Pb
5636
7.76
0.962
<0.075
0.072
1246
20.3
16.3
<0.05
«0.005
Mn
997
7.32
2.33
0.004
0.003
247
4.15
7.18
<0.001
<0.001
HI
110
0.396
0.372
0.0225
<0.015
22.0
0.241
0.346
<0.015
<0.015
Zn
14436
224
38.9
0.036
0.083
2010
38.5
55.8
<0.003
0.0031
AS
36.3
-0.01
0.024
<0.01
<0.01
6.3
<0.01
0.020
<0.01
<0.01
Hg
26.3
<0.008
<0.008
<0.04
<0.02
6.3
<0.008
<0.008
<0.02
<0.02
Quench Wattr •mg/L
Groundwattr Wattr mg/L
0.09 0.016 0.185 1.48 5.005 0.1355 0.009 5.475 0.011 0.0117 O.i
<0.005 0.0067 0.0086 2.39 <0.050 0.107 <0.018 0.029 <0.010 <0.0002 <0.
FACILITY 8
Samp It
Typt
Fly Ash
Fly Ash
Fly Ash
Fly Ash
Fly Ash
BottM Ash
BottM Ash
BottM Ash
BottM Ash
BottM Ash
Field Ltachatt
Qutnch
Groundwtttr
Samp It
Matrix
Solid
EP Tox.
TCLP
SW924-EX1
SW924-EX2
Solid
EP Tox.
Tap
SW924-EX1
SH924-EX2
Wattr
Wattr
Wattr
Units
mg/kg
mg/L
mg/L
•g/L
mg/L
«g/kg
•g/L
•g/L
•g/L
•g/L
•g/L
mg/L
mg/L
Cd
349
18
17.2
<0.01
0.033
10.74
0.388
0.418
<0.01
«0.0l
0.018
0.0025
0.0081
Cr
94.3
•cO.OOS
<0.005
0.0086
0.01
61.2
0.15
0.439
<0.005
<0.005
0.0097
0.019
0.0054
Cu
765
0.171
0.078
<0.005
0.012
4209
0.127
0.018
0.0089
«0.005
0.0973
0.0363
0.012
Ft
12742
0.060
0.019
«O.OOS
0.118
39140
21.0
52.8
-------
TABLE 5.9 SUMMARY RESULTS FOR METALS
FACILITY C
Sample Sample
Type Matrix
Fly Ash Solid
Fly Ash EP Tox.
Fly Ash TaP
Fly Ash SW924-EX1
Fly Ash SW924-EX2
Bottom/Fly Solid
Bottom/Fly EP Tox.
Bottom/Fly TCLP
Bottom/Fly SW924-EX1
Bottom/Fly SU924-CX2
Perimeter Comp. Solid
Field Leachate Water
Quench . ... Water. .
Groundwater Water
Sample Sample
Type Matrix
Fly Ash Solid
Fly Ash EP Tox.
Fly Ash TaP
Fly Ash SW924-EX1
Fly Ash SU924-EX2
Bottom/Fly Solid
3otton/Fly EP Tox.
Bottoei/Fly TaP
SottOM/Fly SW924-EX1
Bottoa/Fly SW924-EX2
Perimeter Coop. Solid
Field Lwcnate water
Quench Water
units
mg/kg
mg/L
mg/L
mg/L
mg/L
mg/kg
mg/L
mg/L
mg/L
mg/L
mg/kg
mg/L
mg/L..
mg/L
Units
mg/kg
mg/L
mg/L
mg/L
mg/L
•J/kg
mg/L
mg/L
mg/L
mg/L
mg/kg
mg/L
mg/L
Cd
173.2
7.89
3.36
0.122
-0.01
17.8
0.06
3.32
<0.01
<0.01
8.7
0.0117
0.128
<0.010
Cd
226.6
8.89
9.6
0.015
<0.01
24.2
0.649
0.025
<0.01
<0.01
30
0.0188
1.335
Cr
55.8
0.038
0.129
0.006
<0.005
87.2
0.0059
<0.005
-------
The analytical results for the metals in the landfill perimeter
composite were expected to approximate the results for the combined ash
samples from the corresponding facilities. Although some slight
variations were noted, the data in Table 5.9 showed that the metals
concentrations for the perimeter composite and combined ash samples were
approximately equal. The slight variations can be attributed to the
effects of weathering on the older ash, the heterogeneity of the ash
materials, and the variability of the raw refuse that is incinerated at
the facility. These observations suggest that the amount of leachable
metals present in the disposed ash is a relatively small percentage of
the total metals.
The quench water at all four facilities is discharged to the local
publicly owned treatment works (POTW). In general, the analyses of the
quench water samples indicated that the quality of the quench water was
suitable for discharge to a POTW. However, the quench water from
Facility 0 had extremely high concentrations of metals because the
samples were collected from the quench water tank and contained an
appreciable quantity of solid materials.
Field leachate samples were collected from natural seeps at three
facilities of the four facilities tested. The leachate discharges are
not controlled or treated at any of the facilities. Therefore, they
eventually percolate into the ground or flow into nearby surface waters.
The field leachate data in Table S.9 showed that the metals
concentrations at all three facilities were essentially equal, despite
the fact that the solid samples of the ash materials disposed at the
three landfills contained significantly different metals concentrations.
This suggests that the leachable metal components in the ash do not vary
in direct proportion with the total metals concentration.
A comparison of the metals concentrations in the quench water and
field leachate showed that the field leachates generally contain slightly
higher concentrations of metals. This suggests that the metals leach
5-17
-------
slowly from the landfills at a relatively constant rate, and that they
usually are not leached in the quench water tank.
The laboratory-prepared leachate metals data in Table 5.9 indicated
that the EP and TCLF methods are more aggressive for extracting metals
than the SW-924 procedure. This was expected because an acidic leaching
solution is used for both the EP and TCLP methods, while in the SW-924
procedure, a neutral leaching solution (i.e., deionized water) is used.
The EP and TCLP procedures appeared to have approximately equal
extraction efficiencies for cadmium, copper, iron, nickel, zinc, mercury,
and selenium. The EP method appeared to extract lead slightly more
efficiently than the TCLP method, but the TCLP method appeared to be
slightly more efficient for extracting arsenic, chromium, and manganese.
Upon comparing the laboratory leachate metals data for the fly ash
with the combined ash and bottom ash, the following trends were noted.
Although the fly ash solids contained higher concentrations of cadmium,
chromium, lead, nickel, and zinc than the combined ash and bottom ash
solids, the fly ash leachates contained higher concentrations than the
combined ash and bottom ash leachates for cadmium. This suggests that
the leachable fractions of chromium, lead, nickel, and zinc are inherent
in the bottom ash. Similarly, the combined ash and bottom ash solids
exhibited higher concentrations of copper and iron than the fly ash
solids. However, the combined ash and bottom ash leachates contained
higher concentrations than the fly ash leachates for iron. This
indicates that the component of the total 'copper is inherent in the fly
ash. Finally, the total manganese concentrations were approximately
equal for the fly ash solids and the bottom ash and combined ash solids;
however, the combined ash and bottom ash leachate contained slightly
higher manganese concentrations than the fly ash leachates. Therefore,
the leachable fraction of manganese appears to be inherent in the bottom
ash.
A comparison of the metals concentrations in the field leachates
with those in the laboratory-prepared leachates showed that the EP and
5-18
-------
TCLP methods approximated the natural leaching conditions for chromium,
copper, iron, nickel, arsenic, mercury, and selenium better than the .
SW-924 procedure. Conversely, the SW-924 procedure appeared to better
correlate with the natural leaching conditions for cadmium, lead,
manganese, and zinc.
For the ground-water metals data, the concentrations were generally
negligible for all metals except iron. Therefore, it does not appear
that the natural field leachate is having a deleterious effect on the
ground water. However, no ground-water data were available to describe
background (i.e., upgradient from the landfill) conditions. At each
facility, with the possible exception of Facility C, the quality of the
monitoring wells systems including the design and locations of the
monitoring wells may not have been adequate to detect releases from the
landfill areas. Therefore, the actual magnitude of the natural
leachate's effect on the ground water could not be discerned.
5.2.2 Polychlorinated Biphenyls, Polychlorinated Dibenzo-p-dioxins,
and Polychlorinated Dibenzo-furans
The analytical results for the PCBs, PCDDs, and PCOFs are summarized
by facility in Table 5.10. The PCS, PCDD, and PCOF results for the solid
samples showed that the fly ash consistently contained higher concentra-
tions of PCBs, PCDDs, and PCDFs than the combined ash and bottom ash.
The data also showed that the PCDDs were generally more concentrated than
the PCDFs and the PCBs in all sample types. Similarly, the PCDFs were
much more concentrated than the PCBs for all sample types;
The field water sample results indicated that negligible quantities
of PCBs were present in these matrices, and only minor quantities of PCDDs
and PCDFs were identified. This suggests that the PCBs, PCDDs, and PCDFs
are not mobile in the natural environment through aqueous transport
pathways. The PCDD and PCDF results for the TCLP- prepared laboratory
leachates were not presented in Table 5.10 because they were generally
near, or below, the detection limit. This suggests that the TCLP does
not extract PCDD and PCDF constituents effectively.
5-19
-------
TABU S.10 SUMMttY RESULTS FOR PC3*. OIOXINS AND FURAHS
Plant
A
A
A
Plant
A
A
A
A
A
A
Plant
8-
3
3
8
Plant
B
3
8
a
a
a
a
a
Sa*ple
Type
Fly Ash
Bottom/Fly
Quench
Sanple
Typt
Fly Ash
Fly Ash
3otton/F1y
3ottan/Fly
Quench
Quench
Sample
Type
Fly Ash
Bottom Ash
Quench
Field Leachate
Sane I «
Type
Fly Ash
Fly Ash
Sottoai Ash
Bottom Ash
Quench
Quench
Field Leachat*
Field Leachat*
Suple
Matrix
Solid
Solid
Water
Sanple
Matrix
Solid
Solid
Solid
Solid
water
Water
Sanple
Matrix
Solid
Solid
Water
water
Sample
Matrix
Solid
Solid
Solid
Solid
water
water
Water
Water
Units
ng/g
ng/g
ug/L
Units
ng/g
ng/g
ng/g
ng/g
"9/1
ng/1
Units
ng/g
ng/g
ug/L
ug/L
Units
ng/9
ng/g
ng/g
ng/g
ng/1
ng/1
ng/1
ng/1
Species
Oloxln
Furan
Oloxln
Furan
Oloxln
Furan
Species
Oloxln
Furan
Oloxln
Furan
Oloxln
Furan
Oloxln
Furan
MONO
-CB
0.64
2,3,7,3
0.16
0.14
5.09
<0.08
2.1
MONO
-CB
0.40
0.03
2.3.7.8
0.35
0.03
0.10
<0.07
<0.08
0.28
3.7
01
-CB
0.73
0.66
0.004
TETRA
4.32
43.6
5.57
39.10
2
12
0!
-CB
1.19
TCTTU
10.90
80.4
0.17
0.49
«0.07
-------
TABLE 5.10 SUMMftY RESULTS FOR PCBs. OIOXINS AND FURANS
Plant
C
C
C
C
C
C
Plant
C
C
C
C
C
C
C
C
C
C
Plant
0
0
0
0
0
Plant
0
D
0
0
0
0
0
0
0
0
Sarnie
Typt
Fly Ash
Bottom/Fly
Perimeter Comp.
Quench
Field Leachate
GroundMtar
Sample
Typt
Fly Asn
Fly Asn
Bottoa/Fly
Botton/Fly
Ptrlmttr Com.
Ptrlmttr Coop.
Quench
Qutncn
Fit Id Leachate
Fit id Ltachatt
Sample
Typ«
Fly Asn
Bottm/Fly
Ptrlmttr Coop.
Qutncn
Fitld Ltachate
Sample
'too
Fly Ash
Fly Asn
8ottO«/Fly
Botton/Fly
Ptrlmttr Com.
Ptrlmttr Com.
Qutncn
Qutncn
Fit Id Ltacnatt
Fitld leacnatt
Sam It
Matrix
Solid
Solid
Solid
water
water
water
Sample
Matrix
Solid
Solid
Solid
Solid
Solid
Solid
water
water
Hater
water
Sample
Matrix
Solid
Solid
Solid
water
Water
Samlt
Matrix
Solid
Solid
Solid
Solid
Solid
Solid
Water
Hater
Hater
Hater
Units
ng/g
ng/9
ng/g
ug/L
ug/L
ug/L
Units
ng/g
ng/g
ng/g
"9/9
ng/g
ng/g
ng/1
ng/1
ng/1
ng/1
-
Units
ng/g
ng/g
ng/g
ug/L
ug/L
Units
"8/9
ng/g
ng/g
ng/g
ng/g
ng/g
ng/1
ng/1
ng/1
ng/1
Species
Oloxin
Furan
Oloxin
Furan
Oloxin
Furan
Oloxin
Furan
Oloxin
Furan
Species
Oloxin
Furan
Oloxin
Furan
Oloxin
Furan
Oioxin
Furan
Oloxin
Furan
MONO
-CB
0.02
2.3,7.8
1.95
13.3
0.36
1.79
0.07
0.51
<0.31
0.55
1.6
11
MONO
-C3
0.94
2,3,7,8
0.54
0.07
0.56
0.15
1.3
17
99
<0.26
0.4
01
-CB
0.65
41.5
0.002
TETRA
27.2
102
6.50
11.42
1.2
2.4
0.59
2.4
28
65
01
-CB
4.00
0.71
0.689
TETRA
9.64
57.6
0.75
3.48
2.5
11
700
590
0.27
2.9
TRI
-CB
225
PENTA
500
152
25.8
12.50
5.7
3.9
5.9
4
93
64
TRI
-CB
3.91
6.52
2.36
0.008
PENTA
59.4
33
2.70
2.63
6
7.7
650
460
<0.22
2.4
TETRA
-CB
109
HEXA
2299
635
37.4
16.54
6.8
4
10
6.2
130
76
TETRA
-CB
2.48
16.50
1.54
HEXA
90.4
69.4
2.03
2.10
4.1
5.3
450
390
2.1
1.9
PENTA
-CB
HEPTA
1837
281
61.6
16.80
9
3.3
19
6.5
172
60
PENTA
-CB
2.25
HEPTA
50.0
47.6
1.95
1.34
4.2
2.7
420
280
8.3
1.2
TOTAL
PCB
0.65
0
375.5
0.02
0.002
0
OCTA
1782
128
44.3
4.08
6.1
0.31
12
1.4
120
15
TOTAL
PCS
11.41
3.42
4.589
0
0.008
OCTA
55.4
5.4
1.63
0.33
3.9
0.61
330
68
25
0.81
TOTAL
6445
1297
176
61.34
28.8
14.41
47.49
20.5
543
280
TOTAL
265
213
9.02
9.86
20.7
27.31
2550
1788
36.17
9.21
TCOO *
TCDF
7742
237
43.21
67.99
823-
TCDO «•
TCOF
478
13.38
43.01
4338
45.28
5-21
-------
Two observations were noted from a comparison of the PCS, PCDD, and
PCDF results for all of the sample types. First, there appeared to be an
inverse relationship between the PCB and PCDD/PCDF concentrations (i.e.,
as the concentration for one of the constituents increased, the concentra-
tion for the other constituent decreased). Second, the PCDOs and PCDFs
appeared to be directly proportional (i.e., as the concentration for one
of the constituents increased, the concentration for the other constituent
increased), although there did not appear to be any relationship between
the relative abundance of either PCOOs or PCDFs in the total PCDD/PCDF
concentration. These observations suggest that the favorable conditions
for PCDD and PCDF formation are similar, while the favorable conditions
for formation of PCBs are unfavorable for the formation of PCDOs and PCDFs.
5.3 Relationships Between Facility Design and Operating
Characteristics and Contaminant Concentrations
In this section, the trends observed in Section 5.2 were evaluated
with the facility design and operating characteristics in an attempt to
explain the trends. Section 5.3.1 presents the evaluation for the metals
data, and Section 5.3.2 presents the evaluation for the PCB, PCDD, and
PCDF data.
5.3.1 Metals
There did not appear to be any significant correlation between the
operating characteristics of the facilities and the metals concentrations
in the residue. In general, the concentration of metal in the residues
is a function of the raw refuse (i.e., incinerator feed material)
composition. Although the distribution of metals between the fly ash and
bottom ash did not appear to be a function of the facility operating
characteristics, it did appear to be influenced by design features of the
incinerator. For example, a rotary kiln incinerator with refuse
processing (e.g., crushing or shredding) would be expected to have a
significantly higher concentration of metals in the fly ash than a
reciprocating grate incinerator without refuse processing. This is
expected because crushing or shredding reduce the particle size, and the
5-22
-------
action of the rotary kiln results in autogenous grinding (i.e., the
attrition and impaction between the particles), which also causes reduced
particle size.
5.3.2 Polychlorinated Biphenyls, Polychlorinated Dibenzo-p-dioxins,
and Polychlorinated Oibenzo-furans
Comparisons between operating characteristics/facility design and
PCS, PCDD, and PCDF concentrations in the residues revealed the following
observations. First, the PCS concentrations in both the fly ash and
bottom ash increased with decreasing incineration temperatures. Second,
the PCS concentrations were higher for the water-wall grate incinerators
(Facilities B and 0) than for the other facility types. Third, both the
total PCDDs and the individual PCDD homologs increased in the fly ash as
the incinerator temperature increased. Fourth, no correlations were
observed between the facility design and operating characteristics and
the bottom ash concentrations of PCDDs or PCDFs. Finally, the PCDD and
PCDF concentrations for both the fly ash and the bottom ash were the
highest for the combination rotary kiln/reciprocating grate facility
(Facility C), and these concentrations were the lowest for the water-wall
grate facilities (Facilities B and D), where the concentrations between
facilities were approximately equal.
5.4 Overall Assessment of Risk
The risks associated with current MWC facility practices were
assessed based on comparisons with applicable standards and criteria.
Section 5.4.1 provides the comparisons for the metals data.
Section 5.4.2 presents an evaluation of the risks associated with the
PCBs found in MWC residues. Finally, Section 5.4.3 presents the risk
assessment for the PCDDs found in MWC residues.
5.4.1 Metals
The results of the fly ash and combined bottom/fly ash and bottom
ash samples prepared by the EP and TCLP procedures were compared to the
RCRA Maximum Allowable Concentrations for arsenic, cadmium, chromium.
5-23
-------
lead, mercury, and selenium. The RCRA criteria for these six metals are
as follows: arsenic =5.0 mg/L; cadmium =1.0 ng/L; chromium =5.0 cng/L;
lead = 5.0 ng/L; mercury = 0.2 mg/L; and selenium = 1.0 mg/L. Six fly
ash samples were extracted using the EP method, and these leachates were
analyzed for metals. The results of these analyses (see Table 4.3)
indicated that none of the samples were above the RCRA criteria for
arsenic/ chromium, mercury, or selenium. However, 100 percent (6 out
of 6) of the EP fly ash leachates exceeded the RCRA criterion for
cadmium. The maximum cadmium concentration in an EP fly ash leachate was
13.0 mg/L. Similarly, 33 percent (5 out of 6) of the fly ash leachates
failed the RCRA criterion for lead. The maximum lead concentration was
25.2 mg/L.
Three combined ash and one bottom ash samples were prepared using
the EP method and analyzed. The results of these leachate analyses (see
Table 4.3) showed that all of the EP leachates were below the RCRA
criteria for arsenic, cadmium, chromium, mercury, and selenium. However,
75 percent (3 out of 4} combined and bottom ash leachates exceeded the
RCRA criterion for lead. The maximum lead concentration was 34.0 mg/L.
The results for the TCLP-prepared leachates were similar. For the
fly ash, 67 percent (4 out of 6) of the TCLP leachates exceeded the RCRA
criterion for cadmium, and 67 percent (4 out of 6) of the TCLP leachates
failed the RCRA criterion for lead. The maximum TCLP leachate concentra-
tions for cadmium and lead were 17.2 mg/L and 15.2 mg/L, respectively.
The combined bottom/fly ash and bottom ash TCLP leachate results showed
that 25 percent (1 out of 4) of the leachates exceeded the RCRA criterion
for cadmium, and 75 percent (3 out of 4) of the leachates exceeded the
RCRA criterion for lead. The maximum TCLP leachate concentrations for
cadmium and lead in the combined ash and bottom ash were 3.32 mg/L and
30.1 mg/L, respectively. The metals concentrations in the TCLP leachates
of fly ash, combined ash, and bottom ash were below the RCRA criteria for
arsenic, chromium, mercury, and selenium. Additionally, the metals
5-24
-------
concentrations in the natural field leachates were below the RCRA
criteria for all six metals.
The analytical results for the ground-water samples metals
concentrations (see Table 4.11) were compared to the primary and
secondary drinking water standards. This comparison showed that all of
the ground-water samples contained concentrations significantly below the
primary and secondary drinking water standards for all metals except
cadmium. One ground-water sample (monitoring well 2 at Facility B) had a
cadmium concentration (0.0081 mg/L) that was only slightly below the
primary drinking water standard (0.01 mg/L).
5.4.2 Pol/chlorinated Biphenyls
The EPA (TSCA) classifies solid materials containing PCBs as follows.
If the solid material contains less than 50 parts per million (ppm) PCBs,
it is considered to be non-hazardous and is not a regulated waste. Solid
materials containing between 50 ppm and 500 pptn PCBs must be handled and
disposed as "PCB-containing" materials. Finally, solid materials
containing greater than 500 ppm PCBs must be handled and disposed as
hazardous PCB .waste materials. The PCS analyses of fly ash, bottom ash,
and combined ash (see Table 4.6) in this study showed that the residues
would not be regulated by TSCA based on their PCB content. The maximum
PCB concentration for a fly ash sample was 24.77 ng/g (parts per billion),
and the maximum PCB concentration for a bottom ash or combined ash sample
was 32.15 ng/g. The maximum PCB concentration measured in this study was
375.5 ng/g for a landfill perimeter composite sample. The field water
samples contained negligible concentrations of PCBs.
5.4.3 Polychlorinated Dibenzo-p-dioxins
The National Center for Disease Control has established a level of
1.0 part per billion (ppb) 2,3,7,3-TCDO in solid materials as the
acceptable limit. The analytical results of the solid MWC residue
samples for PCOOs (see Table 4.7) showed that this limit was occasionally
exceeded. Twenty-seven percent (6 out of 23) of the fly ash samples
5-25
-------
contained 2,3,7,3-TCDD concentrations above 1.0 ppb, with a maximum
concentration of 3.9 ppb. Therefore, these materials may be classified
as potentially hazardous wastes and should be treated accordingly.
Interestingly, all six of the samples exceeding the 1.0 ppb 2,3,7,3-TCDD
limit were collected at Facility C. Although there are not any
established standards or criteria for total ?CDDs, several of the fly ash
samples (3 out of 22) had PCDO concentrations greater than 1,000 ppb
(1.0 ppb), with a maximum PCDD concentration of 12,013 ppb (12.0 ppm).
The results for the combined ash, bottom ash, and landfill perimeter
composite samples were below the 1.0 ppb 2,3,7,8-TCDD limit, with a
maximum 2,3,7,3-TCDD concentration of C.78 ppb. Similarly, the PCDO
concentrations for the field water and laboratory-prepared leachate
samples were negligible, with a maximum 2,3,7,3-TCDD concentration of
0.17 ppb and a maximum total PCDD concentration of 2.55 ppb. This second
observation indicates that the PCDDs vigorously adhere to the solid
particles and are not mobile in the natural environment.
5-26
-------
6.0 CONCLUSIONS
The objective of this study was to collect residues from four
municipal waste combustor facilities for chemical characterization. In
order to meet this objective, a step-by-step approach was established.
First, the four MWC facilities were selected based on the criteria
described in Section 3.1.1. Second, the facilities were visited, and the
procedures detailed in Section 3.3 were used to collect the following
samples: fly ash, bottom ash or combined bottom/fly ash, disposed ash
(i.e., landfill perimeter composite), quench water, ground water, and
field leachates. Additionally, laboratory leachates were prepared from
the fly ash and the bottom ash or combined ash samples using the EP,
TCLP, and MWEP (SW-924) procedures. Third, these samples were analyzed
for metals, PCBs, PCOO/PCOFs, and organic constituents (i.e., total
organic carbon, organic scan, and BNAs) using the procedure* outlined in
Section 3.4. Finally, the analytical data was compiled, summarized, and
evaluated. The following conclusions were drawn from the results and
discussion presented in Section 4.0 and the evaluation provided in
Section 5.0.
1. The RCRA Maximum Allowable Concentration for cadmium was
exceeded by 100 percent of the SP-prepared fly ash samples.
However, the cadmium criterion was not exceeded by any of the
EP-prepared combined ash or bottom ash leachates.
2. The RCRA Maximum Allowable Concentration for lead was exceeded
by 83 percent of the EP-prepared fly ash leachates and by
75 percent of the EP-prepared combined ash or bottom ash
leachates.
3. The concentrations of metals in the ground-water samples did
not exceed the primary or secondary drinking water standards.
This suggests that the natural leachates from the landfill have
not had a major, adverse impact on the ground water.
4. The PCS concentrations were less than the 50 ppm limit
established by TSCA for all solid samples. Therefore, the
solid residues would not be classified as hazardous materials
based solely on their PCS content.
6-1
-------
5. The 2,3,7,3-TCDD concentration exceeded the limit of 1.0 ppb
established by the National Center for Disease Control in
27 percent of the fly ash samples. This limit was not exceeded
by any of the combined ash or bottom ash samples.
6. The variability of the contaminant concentrations between days,
shifts, and units at any given facility was significant,
indicating that slight changes in the incinerator feed material
(i.e., the raw refuse) and/or the operating parameters .
significantly effected the quality of MWC residue. The
variability of the contaminant concentrations between the
facilities was extremely large (i.e., the standard deviations
of the concentrations exceeded the average concentrations).
This suggests that the variability of operating characteristics,
facility design, and feed material composition between
facilities has a significant impact on the resultant MWC
residue quality.
7. In general, the weight ratio of bottom ash to fly ash was
approximately 3 to 1 for the four facilities in this study.
8. The quench water at all four facilities was discharged to the
local wastewater treatment plant. Based on the analytical
results for the quench water samples, this appeared to be an
acceptable disposal technique/ because uncontrolled discharges
of quench water to the environment should be prevented.
9. None of the four facilities had a functioning leachate
collection and/or treatment system. However, the landfill at
Facility A was designed and operated to minimize the contact
between the waste and the environment, thereby reducing the
potential for uncontrolled leachate discharges. ' The other
three facilities did not control the discharges of natural
field leachate.
10. There did not appear to be any correlation between the operating
characteristics of the facilities and the metals concentrations
in the residues.
11. The PCB and PCDD concentrations in the solid residues increased
with decreasing incinerator temperature. Conversely, the PCDF
concentration increased with increasing incinerator temperature.
12. The PCB concentrations in the solid residues were the highest
for the water-wall grate incinerators (Facilities B and 0), but
the PCDD and PCDF concentrations were the highest for the
combination reciprocating grate/rotary kiln incinerator
(Facility C) and were lowest for the two water-wall grate
facilities.
6-2
-------
13. The fly ash contained higher concentrations of all metals
except copper and iron than the bottom ash. Therefore.
combining the ash fractions effectively diluted the total
metals concentrations of the fly ash.
14. The fly ash consistently contained higher concentrations of
PCBs, PCDDs, and PCDPs than the combined ash or bottom ash.
However, the combined ash and bottom ash had higher
concentrations of BNAs than the fly ash.
15. The concentrations of the predominant SNA compounds in the
residues were generally near or below the detection limits.
16. The EP and TCLP methods were more aggressive than the MWEP
(SW-924) method for extracting metals. The EP method appeared
to be slightly more efficient than the TCLP method for leaching
lead; however, the TCLP method appeared to be slightly more
efficient than the EP method for extracting arsenic, chromium.
and manganese. The extraction efficiencies of the EP and TCLP
methods were approximately equal for the other metals. None of
the laboratory leaching procedures were efficient for extracting
organic compounds.
17. The results of the EP and TCLP leachate analyses approximated
the natural field leachate analytical results for chromium,
copper, iron, nickel, arsenic, mercury, and selenium. The
SW-924 leachate concentrations for cadmium, lead, manganese,
and zinc approximated the natural field leachate concentrations.
18. The leachable fraction of the total copper appeared to be
inherent in the fly ash, and the leachable fractions of the
total chromium, lead, manganese, nickel, and zinc appeared to
be inherent in the bottom ash.
19. The contaminant concentrations of the disposed ash (i.e., the
landfill perimeter composites) and the combined ash were not
significantly different. This suggests that the concentration
of the soluble (i.e., leachable) fraction of the contaminants
compared to the total constituent concentrations is minimal.
20. The concentrations of PCBs, PCDDs, PCOFs, and BKXs were
negligible in the field water and laboratory-prepared leachate
samples. Therefore, these compounds appear to be relatively
immobile in the natural environment.
21. The QA/QC objectives for sampling and analysis in this study
were generally achieved. Although EPA/EMSL is currently
improving the analytical method for PCBs in ash samples, some
problems (e.g., low surrogate spike recovery) were encountered
with these analyses.
6-3
-------
22. All of the data generated in this study was comparable to the
results from previous studies.
23. The toxicity Characteristic Leaching Procedure (TCLP) was
ineffective for extracting the organic constituents including
PCDOs, PCDFs, and BNAs.
6-4
-------
APPENDIX A
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-------
2.0 REVIEW OF PERTINENT LITERATURE
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17. Cundari, X. L. and J. M. Lauria. " Laboratory Evaluation of
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19. Czuczwa. J. H. and R. A. Kites. "Environmental Fate of
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A-2
-------
22. Ouekatt. E. J. "Plant Saiaaiona-Dioxina in Perapective:
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24. Eicaaan. G. A., R. E. Claaant. and F. W. Xaraaak. "Variation*
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26. Enginaaring Scianca. Suaaarv of MSM Incinerator Aah Survey.
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27. EPA. Dioxin Analvaia of Philadelphia Northwaat Ineinaratort
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68-01-6671. Work Aaaignaant No. 6O, Auguat 1966.
31. Genetalii, S. J.. 0. Oorfaan, T. J. Concannon. J. Cirello, and
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32. Giordano, P. M.. A. 0. Bahel. J. I. Lawrence. J. M. Solleau.
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A-3
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33. Greenberg, **. &•• <*• &• Gordon, K. J. Yost., at. al.
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34. Greenberg, R. R., W. H. Zoller, and G. E. Gordon. "Coapoaition
and Size Diatributiona of Partielee Releaaed in Refuaa
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No. 5, Hay 1978, pp. 366-373.
33. Haile, C. L., et. al. Aaaeaament of Eaimmiona of Specific
Coaoounda from a Reaouree Recovery Municipal Incinerator.
U.S. EPA, Report No. EPA-360/3-34-002, Hay 1964.
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Utilization of Municipal and Utility Sludqea and Aahea. Volume
IV. Municipal Incinerator Reaiduee (FINAL). National
Environaental Reaearch Center, Cincinnati, OH. Report No.
EPA-670/2-73-033d, Hay 1973.
37. Heimburg, R. V., A. R. Colella, 0. Jonee, J. M. Rauach, and H.
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38. Hinchey, H. 0. Reaeuree ftacoverv and Solid tfaate Hanaqeaent in
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Manageaent, Albany, NY. 1983.
39. Jellua, E., A. X. Thorarud, and F. W. Karaaek. "Two-
dlaenaioaal Elactrophoreaia for Determining Toxicity of
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41. Kenahan, C. B., P. M. Sullivan, J. A. Ruppert, and S. F. Speno.
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42. Xnudson, J. C.. Study of Municipal Incinerator Residue and Ita
Deaiqnation aa a Danoeroua Waate. State of Washington,
Department of Ecology, Solid Waste Section, 1966.
A-4
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43. Kooke. R. H. H., J. W. A. Luatanhouwer. «nd 0. Hutzinger.
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44. Lampsrski, L. L. and T. J. Nestrick. "Determination of Tatra-.
Haxa-, Hepts-, and Octachlorodibenzo-p-dioxin laoaera in
Particulate Samples at Parts per Trillion Levels." Analytical
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49. Law, S. L. "Dissolved Metals in Aqueous Effluents froa
Municipal Incinerators." Journal of the Water Pollution
Control Association. Vol. 49, No. 12. December 1977. pp. 2433-
2466.
46. Law. S. L. and G. S. Gordon. "Sources of Metals in Municipal
Incinerator Emissions." Environmental Science & Technology.
Vol. 13. No. 4, April 1979. pp. 432-436.
47. Lo. Tssi Hong. "Dispossl of Municipal Solid Wastes By
Incineration in Hong Kong." Conservation and Recycling. Vol.
7, Nos. 2-4. 1964. pp. 73-62.
46. Lustenhouwer. J. W. A.. K. Olie. and 0. Hutzinger.
"Chlorinated Dlbenzo-p-dioxlns and Related Compounds in
Incinerator Effluents: . A Review of Measurements and Mechanisms
of Formation." Chamoaphare. Vol. 9, I960. pp. 901-922.
49. Mssksrinec, M. P., C. W. Francis, and J. C. Goyert. "Mobility
of Organic and Inorganic Constituents from Energy and
Combustion-related Wastes Under Codispossl Conditions."
Material Reaeareh Society Svmaeaia Proceedinoa. Vol. 43, 1969,
pp. 227-239.
30. Maynard. T. R. "Incinerator Residue Dispossl in Chicago."
Proeaedinga of the Conference on Geotaehnieal Practice for
Diapeaal of Solid Waste Matariala. ASCS. 1977. pp. 773-793.
31. Mike, J. S. and W. A. Feder. RESCQ Incinerator Reaidue
Reaeareh Program Final Report; Results. Evaluationa. and
Recommendations. Suburban Experiment Station. University of
Massachusetts, 1969.
32. NU3 Corporation.
Municipal Landfill Laaehata Chagaetariatiea. U.S. EPA/OSW,
Washington O.C. Contract No. 64-O1-7310, Work Aaaignaant No.
04, September 1966.
S3. Ogden Project*, Inc. Reaidue Saaa^ina and Analvaia-Harion
County Solid Wa*ta-to-Enarqv Facility. Ogden Martin Syataa* of
Marion. Inc. Report No. 116, December 1966.
A-5
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34. Qlie, X., P. L. Vermeulen, and 0. Hutzinger. "Chlorodibenzo-p-
dloxin* and Chlorodibenzofuran* Are Trace Component* of Fly Aah
and Flue Ga« of Some Municipal Incinerator* in the
Netherland*." Chemoanhare. No. 8. 1977, pp. 433-439.
S3. Ozvacic, V., G. Wong, H. Toaine, R. E. Clement, and J. Oaborne.
"Emiaaion of Chlorinated Organic* from Two Municipal
Incinerator* in Ontario." Journal of the Air Pollution Control
Aaaoeiation. Vol. 39, No. 8, 1969. pp. 849-699.
56. Parker, F. G., J. C. Ouggan, and T. M. Cathcart. Report
Summary! Sumner County Solid-Waate Energy Recovery Facility.
Vol. 2: Performance and Environmental Evaluation. Tennessee
Valley Authority and Electric Power Research Inatitut*. Palo
Alto, CA. 1969.
37. Pohland. Frederick G. and Stephen R. Harper. Critical Review
and Summary of Laaehata and Gaa Production from Landfills.
U.S. EPA/HWERL: Cincinnati, OH. Agreement No. CR8O9997.
38. Port Authority of NY 6 NJ. Resource Reeovagy Raaidua; Rauaa
and Piappeal. Engineering Oept., Oe«ign Division*, Office* of
the Chief Civil Engineer and Chief Mechanical Engineer. Port
Authority of NY 6 NJ, 1963.
39. PRC Engineering. Characterization of Municipal Solid Waata In
The United State* 196O-2OOO. U.S. EPA/OWPE, Weahington D.C.
Contract No. 68-01-7037. Prepared by Franklin Aaaoc. for PRC.
July 23, 1966.
60. Rademaker. A.O. and J. C. Young. "Leachata* From Solid Waata
Recovery Operation*." Journal of the Energy Division. ASCE,
May 1981, pp. 17-29.
61. Rappe, C. "Analysis of Polychlorinated Dioxins and Furans."
Environmental Science & Taehnolocv. Vol. 18, No. 3, 1984, pp.
78A-9OA.
62. Rappe. C. and H. R. Buser. "Polychlorinated Dioxina and
Oibenzofurans in Incinerator Effluents.** Manuscript, 1981.
63. Rsppe, C., 9. Merklund, A. Bergqvist, snd M. Hsnsson.
"Polychlorinated Dibenzo-p-dioxins, Oibenzofursns. and Other
Polynuclear Aromstics Formed During Incineration and
Polychlorinated Biphenyl Fires.** Chlorinated Dioxins and
Dibenzofurans in the Totsl Environment. Vol. 1, Ann Arbor, MI:
Ann Arbor Science Publishers. 1963.
64. Redford, 0. P., C. L. Haile, and R. M. Lucas. "Emissions of
PCOOs and PCDFs from Combustions Sources." The International
Symposium on Chlorinated Oioxins and Related Compounds,
Arlington, VA. October 23-29, 1981.
-------
69. Rghai, Had! Oaar. Phvaieal and Chaaiefl^ Bahavior of
Chlorinat.ad Dioxina on Fly Aah froa Munieia*^ Ineinarator».
. Diaaartation, Naw H«xieo Stata University, L«« Crucaa, NM>
66. Rigo, H. G. Stata-of-tha-Xnowladoa Raoort. on tha Diaeoaal of
Inelnarator Aah. Rigo and Rigo Aaaociataa, Duxbury, HA. 1962.
67. SAXC-Braalatt, J., at. al. Coapoaition of Laaehataa Froa
Ae-fcual Hagardoua Maata Sitaa. U.S. EPA* Waahington O.C.
Contract. No. 66-03-3113, Work Aaaignaant No. 39-7.
66. Schoanbargar, R. and J. Bandar. "Analyaia of Matala Found In
Incinarator Raaidua." Proeaadlnoa of tha 1976 National Waata
Proeaaaino Ccnfaranea. ASMS. 1976* pp. 499-911.
69. Schoanbargar. R. J. and A. A. Fungaroli. "Incinarator-Raaidua-
FiH Sita Invaatigation." Journal of tha Soil Maehaniea and
Foundation* Divlaian. 1971, pp. 1431-1443.
70. Schoanbargar, R. J. and P. W. Purdoa. "Long Tar» Chaaical
Laaching From Incinarator Raaidua." Proeaadinaa a-f tha 1976
National Waata Proeaaaino Con£aranea. ASMS, 1976, pp. 469-497.
71. Schaub, W. H. and W. Taang. "Dioxin Formation in
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No. 12, Dacambar 1982, pp. 721-73O.
72. Skinnar 6 Sharaan Laboratoriaa. Taehnieal Raoort. Praoarad For
Rafuaa Snarqy Svatana Coaoanv (RS3CQ). Skinnar 6 Sharaan
Laboratoriaa, Wathaa, HA. 1962.
73. Surgi, R. "Raaiduaa Froa Raaourca Racovary Facilitiaa:
Currant Raaaarch." Papar praaantad for Signal Environaantal
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Naw York, Stony Brook, NY 1966.
74. Taylor, 0. R., H. A. Toapkina, S. S. Kirton, and D. F. S.
Natuach. "Analyaia of Fly Aan Producad froa Coabuation of
Rafuaa-Darivad Fual and Coal Hixturaa." Snvirpnaantal Seianea
& Taehnalaqv. Vol. 16, No. 3, 1962, pp. 146-194.
79. van dar Sloot, H. A., 0. Piapara, and A. Kok. Standard
Laaehina Jaat for Coabuation Raalduaa. Studiagroap
Ontwikkaling Standaard Uitloogtaatin Varbrandingaraaiduan
(SOSUV), Natharlanda, 1964.
76. Uaklaoto, T. and R. Tataukawa. "Polychlorinatad Oibanzo-p-
dioxina and- Dibanzofurana in Fly Aah and Cindara Collactad froa
Savaral Hunicipal Ineinaratora in Japan." Enviro'naantal Haalth
ParaaaetlvM. Vol. 99, 1969, pp. 199-162.
A-7
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77. Wallinga, R. A. . "That Coapoaition of Raalduaa from Municipal
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Jun« 1974. pp. 294-302.
78. Wilaon. E. B. and 0. J. Akara. "Chaaical and Phyaical
Charactarization of Hatropolitan Zncinarator Rafuaa and
Flyaah." Pyoeaadinaa of t.ha Saeond Mineral Waata Ut.iligatlon
Svaaoaiua. Chicago, IL 197O, pp. 313-326.
A-8
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APPENDIX B
ANALYTICAL METHODS FOR PCDD/PCDFs
-------
ANALYTICAL PMCCDUXC3 TO ASSAY STACX CFFluCKT
•
ANQ RESIDUAL COWUSTIQH PRODUCTS TO*
OIIO20-P-010XDIS (K90) AND POLYCXIORMATEO OHEHZOFUIUNS (PCOF)
1. Scop« «nd Applicability of Method
Tho analytical procedures described hart «rt applicable for the
determination of polychlorlnatad dlbenio-p-dloxlnj (PC90) and dlbenzo-
furam (PCDF) In stick effluents fro» comftustlon processes. These methods
•rt Also applicable to residual cooftustlon products such as bottom and
predpltator ash. Tho methods presented entail addition of fiocaplcally-
laboled Internal standards to all saapl«s in known quantltlts, extraction
of tfco s«p1t «1tn appropriate organic solvents, pr«llainary fractlonatlon
and cleanup of tht extracts usln? a sequence of liquid cnronatography
eslMns* and analysis of the processed extract for PCOO and PCOF using
coupled 9*s dirwatoorapny - ous spectrwetry (GC-MS). Various
performance criteria are specified herein «nich the analytical data
eust satisfy for quality assurance purposes. These reoresent «ln1imji
criteria Nhlcft oust bo Incorporated Into any proertsi 1n «n1ch K80
and PCOF are dotanrined 1n covaustlon product saaples.
Tho Mthod presented hero does not yield definitive Information on
the concentration of Individual PC80/PC3F Isoners, except for 2,3,7,1-
TctrachlQrod1b€nzo-p-41ox1n (TOO) and 2,3,7,8-Tetrachlorod1ben2ofuran
(TOP). Rather, It Is designed to Indicate the total concentration of
tht Isoaers of several chlorinated classes of K80/PC8F (that Is. total
tatra-, penta*, noxa*, hepta-, and octachlorfnatad 41benxo*p-d1ox1ns and
dlbenxofurans). Of the 79 separata PCOO and US ?CDF IsoMrs, there
are 22 TCSO, 38 TC8F. 14 PeCOO. 2S PeCOF, 10 MxCOO, 16 HxCOF. 2 HpCOO,
4 HpCOP, 1 OCSO and 1 OC8M
Tho analytical oothod presented herein 1s Intended to be applicable
for determining PCOO/PCOF present 1n coveustlen products at the ppt to
ppa level, but the sensitivity «*1ch can ultimately be achieved for a
given saaple will depond upon tho types and concentrations of other chealcal
coosounds In the saaple.
Tho aethod described here oust bo Implemented by or under the
supervision of cheerists with experience m handling supertoxlc materials
and analyses should only bo performed 1n rigorously controlled. Halted
access laboratories. Tho quantltatlon of PCflO/KDF should bo accomplished
only by analysts experienced 1n utilizing capillary-column gas chreoatograpny.
mass spectroeatry to accomplish quantltatlon of chlorocarbons and similar
compounds at very lev concentration.
B-l
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toxlcologlcal data which art available for tht PCOO and PCOF »rt
far from complete. That Is, tht toxlcologlcal properties of all of
tfte Isomirs comprising tht 75 posslbit PCOO and US posslbit PCOF art
not prtstntly known. However, a consldtrablt body of toxlcologlcal
data txlsts for 2,3,7.<-TC80 which 1nd1catas that, 1n certain animal
species, this compound Is lethal at extraordinarily low do«s and causas
a wldt rangt of systemic afftcts. Including hepatic disorders, carcinoma
«n4 birth defects. Millt euch Itss data 1s avallabit regarding tht
toxicology of 2.J,7,f-TW. sufficient data 1s avallabit to fora tht
basis for tht btlltf that 2t3.7,«-TC8r Is similar 1n Its toxlcologlcal
prootrtlts to 2,3,7.f-TC80. Relatively little Is known about tht toxi-
cology of tht higher chlorinated PC80 and PCSf (that 1s, pent* through
octachlorfnated PCOO/PCOFh although there Is some data to suggest that
certain pent*-, htxa-, and heota* PCM/POJF Isomers are haiardous. In
v1e« of the extraordinary toxlclty of 2,3,7.8-TCaO and 1n view of tht
exceptional biological activity of this coapound (on the basis of enzyme
Induction assays ) and of compounds having similar nolecular structures,
extensive precautions are required to preclude exposure to personnel
during handling and analysis of materials containing these compounds and to
prevent contaertnatlon of the laboratory. Specific safety and handling
procedures which are receamded are given In the Appendix to this protocol.
a.
The abbreviations which are used to designate chlorinated d1benzo-p-
dloxlns and dlbenzofurans throughout this document are as follows:
PCOO • Any or all of the 7S possible chlorinated d1ben2O«p«d1ox1n Isoners
POP - Any or all of the 138 possible chlorinated dlbenzofuran Isoners
TC80 - Any or all of the 22 possible tetrachlorlnatad d1benzo-p-d1ox1n isest
TC8F * Any or all of the 13S possible tetrachlorlnatad dlbenzofuran Isemers
PeCSO - Any or all of the 14 possible pentachlorlnatad d1benzo-p-d1oxln fsor-
PeCST - Any or all of the 2S possible pentachlorlnatad dlbenzofuran Uomers
HxCOO • Any or all of tht 10 possible hexachloHnatad d1benzo«p-d1oxln
HXC8T • Any or all of tht II possible hexachloHnatad dlbensofuran
HpCflO - Any or a11 of tht 2 possible heptaehlortnatad d1benzo-p-d1oxln lso«t
HpOV • Any or all of tht 4 possible neptachloHnated dlbtnzofuran Isomers
OC80 - Octach1orod1benzo-p-d1ox1n
OCOP - Octachlorodlbenzofuran
Specific Isomers. - Any of the abbreviations cited above aey be convtrttd t
designate a specific 1 scaur by inoicatmg the exact positions (carton awr
where chlorines are located within the nolecule. For example, 2,3.7,8-««.-a
refers to only one of the 22 possible TCOO Isomers • that Isomer which U
chlorinated In tht 2,3,7,1 positions of tht d1benza-p-diox1n ring structure
B-2
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2. Reagents
The following reagents and chemicals art approprfate for ust 1n thtst
proctdurts. In all casts, tquivaltnt raetrlals from othtr supplitrs
may also be used.
2.1 Potassium Hydroxide, Anhydrous, Granular Sodium Sulfatt and
Su If uric Add (all Reagent Grade): J. T. Baktr Chtmlcal Co. or Flshtr
Scientific Co. The granular sodium sulfate 1s purifltd prior to use
by placing a beaker containing the sodium sulfate 1n a 400 C ovtn for
four hours* then removing the beaker and allowing It to cool In a desiccator.
Store the purified sodium sulfate 1n a bottle equipped with a Teflon-
lined screw cap.
2.2 Hexane, Methyltne Chloride, Benzene, Hethanol, Toluene,
Isooctanc: 'Distilled 1n Glass* Burdlck and Jackson.
2.3 Trldecant (Reagent Grade): Sigma Chemical Co.
2.4 Basic Alumina (Activity Grade 1, 100 • 200 mtsh): IO1
Pharmaceuticals. Immediately prior to use, the alumina 1s activated by
heating for at least 16 hours at 600 C 1n a muffle furnace and thtn
allowed to cool 1n a desiccator for at least 30 minutes prior to use.
Store pre-conditioned alumina 1n a desiccator.
2.5 $111ca (810-S11 A.100/200 mesh): Blo-Aad. The following
procedure 1s recommended for conditioning the B10-S11 A prior to use.
Place an appropriate quantity of Blo-SII A In a 30 ne x 300 m long
glass tube (the silica gel 1s held In place by glass wool plugs) which
1s placed 1n a tube furnace. The glass tube 1s connected to a pre-
puHfled nitrogen cylinder, through a series of four traps (stainless
steel tubes, 1.0 cm 0.9. x 10 cm long)*: 1) Trap No. 1 - Mixture
comprised of Chromosorb U/AU (60/tO nesh coated with SS Aplezon L),
Graphite (UCP-1-100), Activated Carbon (SO to 200 mesh) in a 7:1.3:1.5
ratio (Chromosorb U/AU, Aolezon L obtained from Supelco. Inc.. Graphite
obtained from Ultracarbon Corporation, 100 flesh, 1-M-USP; Activated
Carbon obtained from Fisher Scientific Co.); 2) Trap No. 2 • Molecular
Steve 13 X (60/10 mesh), Supelco, Inc.; 3) Trap No. 3 - Carbosleve S •
(80/100 mash), obtained from Supelco, Inc.; 4) The B10-S11 A Is heated
1n the tube for 30 fllnutes at 180*C while purging with nitrogen (flow
rate 50-100 ml/minute), and the tube Is then removed from the furnace
and allowed to cool to room temperature. Methanol (175 nt) 1s then
passed through the tube, followed by 175 ml methylene chloride. The
tube containing the silica 1s then returned to the furnace, the nitrogen
purge 1s again established (50-100 ml flow) and the tube 1s heated at
50*C for 10 minutes, then the temperature 1s gradually Increased to
iao*C over 25 minutes and maintained at 1SO*C for 90 minutes. Heating
1s then discontinued but the nitrogen purge 1s continued until the tube
B-3
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cools to rooa tewperature. Finally, the silica is transferred to i clean,
dry. 9l4SS bottle- and capped with a Teflon-lined screw cap for storage.
2.5 Silica Sel Iieiregnated With SulfuHc Add: Concentrated sulfuric
add (44 9) 1s cotfclned wirn 100 9 8 Jo-Si 1 A (conditions* as described
afeove) 1n a screw capped beetle and agitated to «lx thoroughly. Aggre-
gates art dispersed with a stirring rod until a unlfone •Ixtun 1s obtained.
TIM HSOj-sllica g«1 1s stored 1n a scr«*- other suppliers nay
also be used.
3.1 Glassware used in the analytical procedures (Including the
Soxhlet apparatus and disposable bottles) 1s cleaned by rinsing successively
three t1e»s with nthanol and then three tlavs with Mthylene chloride,
and finally drying 1t in a 100 C oven. Settles cleaned 1n this Banner
are allowed to cool to roeei tawperature and are then capped using Teflon-
lined 11ds. Teflon cap liners are rinsed as* just described but are
allowed to air-dry. Hare rigorous cleaning of sow glassware with
detergent nay be required prior to the solvent rinses, for exaople. the
glassware ea^loyed for Soxhlet extraction of saaples.
B-4
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3 1.1 Sample Vessels: 125 (it and 250 rt. flint glass bottles fitted
with screw caps and teflon cap liners, and jlass ttst tubes, vwR-Sdencific.
3.1.2 Ttflon Cap Liners: Scientific Specialities Service, Inc.
3.1.3 Soxhlet Apparatus: Extraction apparatus, AlUhn condenser,
Klmax Brand, American Scientific Products Cat. No. E52S2-2A.
3.1.4 Gravity flow Liquid Chromatoeraphlc Columns: Custom
Fabricated (Details of the columns art provided 1n later sections).
3.1.5 M1cro-v1als (3.0 at): Reliance Glass.
3.2 Capillary Gas Chromatoeraohlc Colons: Two different columns are
required 1f data on botn 2.3.7,8-TCOO and 2.3,7,8-TCOF, as veil as on
the total PCOO/PC3F by cnloHnatad class, are desired. The appropriate
columns are: 1) A fused silica ca1t«R (40 N x 0.25 m 1.0.) coated
wltii 01-5 (0.2S u f11> tnlcieness), J 4 S Scientific. Inc., Crystal
Lake, II 1s utilized to separate eacn of tne several tetra«throucn
octacAlorinated COOs and COFs, as a froup, frost all of the otner groups.
While this column does not resolve all of the Isomers within each
chlorinated group, 1t effectively resolves uch of the chlorinated
groups frost all of the other chlorinated groups trd therefore provides
data on the total concentration of each grouo (ttut 1s, total tetra-,
penta-, hexa-, hepta* and octa COOs and COFs). This colum also
resolves 2,3,7,3-TCOO from all of the other 21 TC30 Isocers and this
Isooer can therefore be determined quantitatively if proper calibration
procedures are applied as described further in a later section. This
column does not completely resolve 2,3,7,I-TC3F from the other TC8F
Isoners, and 1f a peak corresponding in retention time to 2,3,7,8-TCOF
1s observed 1n the analysis using this column, tnen a portion of the
saaple extract nust.be reanalyzed using the second GC column described
below If 1 saner • specific data on 2,3,7,S-TC3F is desired. 2) A
fused silica column (30 N x 0.29 m 1.0.) coated with OB-US (0.25 u
film thickness), J 4 S Scientific, Inc., Crystal Lake. IL. oust be
utilized to obtain quantitative data on the sancentratlon of 2,3,7,8-
TCOF, since this column adequately resolves 2,3,7,8-TCOF from the other
TCOF 1s<
3.3 Balance: Analytical Balance, read1b111ty. 0.0001 g.
3.4 nitrogen Slowdown Concentration Apparatus: N-Cvap Analytical
Evaporator Model III, Organematlon Associates Inc.
3.5 Tube Furnace: Lindberg Type 59344.
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4. Instrumentation
841 Chromatograph-Hass Spectrometer-Oata System (GC/MS/OS): The
iMtrumtnt system used ta analyze sample extracts for PCOO/PCOF
coaoMsts a Sis chroaatograph (fitted for capillary columns) coupled
dlntctly or through *n enrichment device to a ntss spectrometer which 1s
•oulooed with « computer-based data system. The individual components
of tht SC/W/OS art described below.
4.1 Sas Chromatograph (SC): Tht Chromatograph out be equipped
vfth an appropMatt injector and pn«uMt1c system to permit use of the
specified glass or fused silica capillary columns. It oust also Incor-
porate an oven which can be nested In a reproducible, programed
tmmjerariin cycle. The Injector should be confloured for spMtless/
split Injections. Tht SC column ptrfoneance should be vertfltd at the
be9lnnln9 of etch 8 hour «orfc ptHod or at the be^lnnln^ of each series
of analyses If tart than ont sot of saaples is analyzed durlne, an I
hour shift. Extracts of coapltx coaoustlon products and effluents nay
contain nuntrous organic rtslduts tvtn after application of tht axtan-
slvt prtfract1onat1on/c1eanuo procedures specified 1n this eithod.
Thest rtslduts aay result 1n strlous dtvlatlon of SC coluan ptrfor-
tance and thtrtfort, frtquent ptrforMnct chtcks art desirable. Using
appropriate calibration Mixtures, as described below, tht retention
t1w windows for each chlorinated class of CSOs/COfs oust bt vtrlfltd.
In addition, tht SC coluan utilized oust bt dtaonstrated to effectlvtly
stparate 2,3,7,3-TCOO fro* all other TOO tsoears If data on 2,3,7,8-
TC80 alont 1s dtslrtd with at least 201 valley definition between the
2,3,7,3- 1somr and tht other adjacent-tlutlnt, TCOO Isoatrs. Typically*
capillary coluan peek widths (at halfntaxlsut peak height) on tht ordtr
of 3-10 seconds art obtained In tht courst of these analyses. An
appropriate GC ttaptraturt prograei for tht analysts described htreln
Is discussed 1n a later section (set Table 1).
4.2 Oas ChroMBtograph-mss Soectroaeter Interface: Tht GC*MS
Interface can Include anrlchaent devices, such as a glass jet separator
or a s111cont oeeferant separator, or tht gas chroemtograph can bt
directly coupled to tht emss sptctronttar source, 1f tht systea ha'*
adequate punplng of tht source region. Tht Interface may Include a
dlvtrter valve for shunting tht coluan effluent and Isolating tht
nass spectrometer source. All coaoontnts of tht interface should be
glass or glass-lined stainless steel. Tht Interface components oust bt
compatible with temperatures 1n tht ntlghbornood of 2SQ*C, which Is Wt
temperature at which tht Interface Is typically maintained throughout
analysts for PCM/POT. Tht O/W Inttrfact mutt bt approprlattly
configured so that tht separation of 2,3,7.1-TCOO from the ethtr TOO
isomtrs which 1s achieved in tht gas chromatogrtphlc coluan is not
appreciably dtgrtdtd. Cold spots and/or actlvt surfaces (adsorption
sites) 1n tht a/W Inttrfact can caust peak tailing and ptak broadening,
If tht latttr art obstrvtd, thorough cleaning of tht Injection port.
interface and connecting lines should bt accomplished prior to pro-
ceeding.
B-6
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4 3 Mass Spactromtar (MS): Tha mass spectrometer used for the
dascrlbad hara 1s typically a double-focusing sactor or
ua Instrument aqulppad with an alactron iap«ct sourca (70 ev),
•alntalnad at 2SO*C, and a standard alactron multiplier datactor.
If Dosslbla, 1t Is desirable to hava both lot* and high resolution
capability with tha mass spectrometer used, slnca confirmation of
data oOtalnad by low resolution MS using high resolution MS 1s sometimes
desirable. Alternatively, a combination of aiss spectrometers can ba
used for this purposa. Tha static resolution of tha Instrument oust
ba Maintained at a minimum of 1:500 (with a 101 valley between ad4acant
•asses) 1f operating In the low resolution MS mode, and a minimum
resolution of 1:10,000 1s desirable for operation 1a the high resolution
•ode. The mass spectrometer mat also be configured for rapid computer-
controlled selected-Ion monitoring 1n both high and low resolution
operating Modes. At a minimum, two lon-evsses characteristic of each
class of chlorinated dloxlns should be monitored, and these are two
Ions 1n the molecular 1on Isotapic clustar. It 1s desirable for
Increased confidence In the data to also aonltor the fragment Ions
arising frooi the loss of COC1 from the molecular Ion. In order to accomplish
the requisite rapid Multiple Ion oanltorlng sequence during the t1«e
period defined by a typically capillary chroaatagraphlc peak (the base
of the chromatogrephlc peak Is typically 15-20 seconds 1n wldtb), the
following MS performance parameters are typically required (assuring
a 4-1on Bonltorlng sequence for each class of POJO/PCOr): dwell t1m/
Ion-mass, »100 msec.; minimum number of data po1nts/chromatagraph1c
peak, 7 . The mass scale of the BBSS spec trow tar 1s calibrated using
high boiling perfluorokerosene and/or soae other suitable ness standard
depending upon the requirements of the GC-MS-OS system utilized. The
actual procedures utilized for calibration of the eass scale will be
unique to the particular mass spectrometer being employed. A 11st of
tha appropriate Ions to be monitored 1n the PCOO/PCOP analyses described
herein 1s presented In a later section (see Table 1).
4.4 Data System: A dedicated computer-based data system, capable
of providing the data described above, 1s employed to control the rapid
selected-Ion monitoring sequence and to acquire the data. Both digital
data (peak areas or peak heights) as well as peak profiles (dlsoUys of
Intensities of Ion-masses monitored as a function of tine) should be
acquired during the analyses, and displayed by the data system. This
raw data (mass chromatagrama) should be provided In the report of tne data.
5. Calibration Standards
A recommended set of calibration standards to be used 1n the analysas
described herein Is presented below. Stock standard solutions of the
various PC90 and PC8F Isomars and mixtures thereof are prepared 1n a
glovebox, using weighed quantities of the authentic Isomers.0 These
stock solutions are contained In appropriate volumetric flasks and are
stared tightly stoppered, 1n a refrigerator. A11quots of the stock
standards are removed for direct use or for subsequent serial dilutions
to prepare working standards. These standards must be checked regularly
(by comparing instrument response factors for them over a period of
a-?
-------
tlat) to tnsurt that solvent tvapor«tion or othtr lossts navt not occurrtd
which Muld iltir tht standard concentration. The stvtril rtconrntndtd
standard solutions art as follows.
j.1 Standard Mixture A: Prtpart i stock solution containing tht
following Isotopically-labtlltd PCOO and PCOF in isooctant it tht
1nd1cattd conctntratlons: 2.Sn«./ttluCu-2.3,7,8-TCOO. 2.5ng/u11TCU-
2.3.7.8-TCOF, ZSntfuL"^-! ,2.3.4,7,8-HxCOO, 25ng/uLlfCia-1 ,2.3.4,7.3-
HxCOF, 2Sng/uLllCia-OCOO,' and 2Sng/uLllCi»-OCOF. Portions of this
Isoatr rixturt in addtd to all sacplts prior to analysts and strvt
as Intamal standards for us« 1n quantltatlon. tacavtry of thtst
standards 1s also usod to guagt tht ovtrail tfflcacy of tht analytical
procodurts.
S.2 Standard 8: Prtpart a stock solution containing 1.0 ng of
>7CU-2,3,7,a-TCOO/uL of isoectant. This standard can bt colnjtcttd
1f dtslrtd, alon? with allquots of tht final sanplt txtract to rtllaoly
tstlHtt tht rtcovtry of tht uCi»-2.3,7,a-TCBO surrocatt standard.
5.3 Standard Mlxturt C: Prtpart a stock solution containing
100 ntVul of Isooctant of tach of tht following PCSO and POP:
2.3.7,t-TC8Fj 2,3.7,«-TCOO; 1,3.4,4,|^«COF, 2.3,4,«,7^«CDF; 1,2.4.7.9-
PtCSO; 1.2.3,8,9-PtC80; 1.2.3.4t«,8.HxCOF; 2.3,4,C,7,i-MxCOF; 1,2.3.4.5.8-
HxCOO, 1,2,3,4,5,7-HxCOO; 1,2,3,4,4,7,3-HoCOf; 1.2.3,4,7J,9-HpCOF;
1,2.3,4,6,7,8-HpCOO; 1,2,3,4,8,7,9-HpCDO; OCCF: and OCOO. This 1sow
«1xturt is ustd to dtflnt tht oas chronatooraphlc rtttntlon tlat
Inttrvals or windows for tach of tht ptnta-, htxt-. htpta-, and
octachlorlnattd groups of PCOO and PCOF. Each pair of Isootrs of a glvtn
chlorlnattd class which Is llsttd htrt corrtsponcs to tht first and
last •luting Isootrs of that class on tht 01-5 capillary SC coluom
(txctpt for TCOO and TCOF). In addition, this Isomtr arixturt 1s ustd
to. dtttnrint SC-MS rtsponst factors for rtprtstntatlvt Isomrs of tach
of tht ptnta-, htxa-, ntpta-, and octachlorlnattd groups of PCOO and
PCOF. Tht lattr data art ustd 1n quantltatlng tht analytts in unknown
sanplts.
5.4 Standard Mlxturt 0: Prtpart a stock solution containing
50 pt/uL of isooctant of tach of tht following TCOO Isomrs: 1.3,6.8-
TCOO; 1.2.3,7-TCOO; 1.2.3.S-TCW; 2.3,7.8-TCOO; and 1,2,8,9-TCOO. Two of tht
Isoatrs In this vfxturt art ustd to dtflnt tht gas chronatogrtphlc
rtttntlon tint window for TCOOs (1,3,8,8-TCOO 1s tht first «luting TCOO
b* SOM of tht PCOO/PCOF 1so«r standards rtcoimndtd for this ttthod
art avallablt froa Cwdrldgt Isotopt UooraCorlts, CaooHdgt, Massachusttts.
Othtr PCOO/PCOF standards art avallablt fro* tht 8rthn Laboratory, Urignt
Statt Unlvtrslty, Oayton, Ohio, fro* tht U.S. EPA Standard Ktposltory
at Rtstarch Trlanglt Part, North Carolina and possibly froa othtr laborttorfts.
Not all of tht Indicattd 1sotop1ca11y-1abt11td PCOO/PCOF inttmal standards
rtcoBMndtd htrt art prtstntly avallablt in quantltits sufficient for
wldtsprtad distribution, but thtst art txptcttd to bt availablt in tht ntar
futurt.
B-8
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Isoaar M* 1,2,3,9-TGO 1s the last tluting TCOO Isoaer on the 08-5
SC cold")* Thi remaining Isomn serve to demonstrate that tht 2,3,7,8
rrgo Isoaar Is resolved froa Urn other nearest (luting TCOO 1 sowers,
tnd that the coluan therefore yields quantitative data for the 2 ,3.7,8-
Isoaar alone.
8.8 Standard Mixture C: Prepare a stock solution containing SO pg/O.
of Isooctane of each of the following TC3F Isoaers: 1,3,8,8-TCOF; 2.3,4,8-
TCOFj 2.3,7.8-TCOf, 2,3,4,7-TCDF; and 1,2.8,9-TCOF. This Isoaar elxture
1s used to define the TCDF gas chroaatographlc retention tlaa window
(1,3,8,8- and 1,2,i,9-TCOf are the first and last elutlng TCOFs on the
08-5 capillary coluan) and to deaonstrata that 2.3,7.8-TCOF 1s uniquely
resolved froa the adjacent-elutlng TCOF iseaers.
8. Procedures for Addition of Internal Standards and Extraction of Samples
Both liquid and solid saaples will be obtained for PCOO/PCOT
analyses as a result of the application of an appropriate stack
saapHng procedure. Saaples
resulting froa the saapllne. train will Include the following (these
will be provided to the analytical laboratory as separate saaples 1n
the fora Indicated): 1) paniculate filter and pertlculatas thereon;
2) particulars froa the cyclone (1f used); 3) ceablned aqueous solutions
froa the laplngers; 4) the Intact XAO-resIn cartridge and the resin
therein; S) coablned aqueous rinse (1f used) solutions froa rinses of
the nozzle, probe, filter holder, cyclone (1f used), laplngers, and
all connecting lines; 8) combined acetone rinse solutions froa rinses
of the nozzle, probe, filter holder, cyclone (If used), laplngers, and
all connecting lines; 7) coeblned hexane rinse solutions froa rinses
of the nozzle, probe, filter, cyclone (If used), laplngers, and all
connecting lines. In addition, saaples of bettoa ash, preclpltator
ash. Incinerator feed mterlals or fuel, quench liquids, and aitarials
froa effluent control devices Bay also be provided for analyses.
In general, the voluaes of all liquid saaples received for analyses
are eeasured and recorded, and where appropriate, solid saaples or
allquots thereof are weighed. Any saaples which are heaogeneous (as
for exaaple, a single liquid phase saaple or a solid which can be
thoroughly mixed) can be split prior to analyses. If desired, provided
that this will still penrit the attainment of the desired detection
Halts for the analytes of Interest. Saaeles such as particulars from
the saapllng train which are generally collected 1n relatively saall
quantity, are preferably analyzed In total.
8.1 Organic Liquid Saaples (Acetone and Hexane Solutions)
Concentrate each of the coabined organic liquids (acetone and hexane
solutions) to a volume of about 1-5 a. using the nitrogen blowdown
B-9
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anoaratus (i stream of dry nltrogan) whilt htatlng tht samplt gtntly on a
water bath. Pool the concantratad reslduts, rinsing tht vtsstls thret
tints with small portions of htxant and adding thtst to tht rtslduts,
and concantrate to naar dryntss. This rtsldut will Hktly contain
oartlculatts which ware rtmovtd 1n tht rinsts of the train probt and
M2z1t. Comblnt the resldut (along with thret rinsts of tht final
iarpi« vtsstl) 1n tht Soxhltt apparatus with tht fllttr and particulars,
and procttd as dtscribtd undtr Solid Saoplt btlov.
1.2 Aquteus Liquids
Add an appropriate quantity of tht Isotoplcally-labtltd Internal standard
•Ixturt (SUndird Mixture A dtscribtd tarlltr) to tht aqutous liquid
swplt (or an aliquot thtrtof} In a scrtwcapptd bettlt fitted with a
Ttf1on»11ntd cap. Add approxlntttly 25X by voluflt of htxant to tht
spited aqutous saoplt, stal tht bottlt and a^ltete on a snaktr for a
ptrlod of thrtt hours. Allow tht vtsstl to stand until tht aqutous and
organic laytrs stparate, thtn transftr tht organic laytr to a stpartte
sa«plt bottlt. Rtptat tht htxant tatraction stqutitct two additional
tlats and cc«o1nt tht organic fractions with that fro* tht first ax*
traction. Procttd with tht saoplt fractionalon and cltanua proctdurts
dtscribtd btlow.
6.3 Solid Sanplts
Plact a glass attraction thlmblt and 1 g of silica gtl and a plug of
glass wool Into tht Soxnltt apparatus, chargt tht apparatus with to1 wit
and rtflux for a ptrlod of ont hour. Rtoavt tht tolutnt and discard It,
retaining tht silica gtl, or 1f dtslred, reteln a portion of tht tolutnt
to chtck for background contamination. For extraction of partlculates,
pi act tht tntlre samp It 1n tht thlrtla ante tht bad of preclaantd silica
gtl (1 cau thick), and top with tht precltantd glass wool reta1nt<»
froai tht Initial Soxhltt cltanlng prectdure. A44 tht appropriate
quantity of tht 1sotep1cal1y-!abtlltd Internal standard mixture
(Standard Mixture A dtscribtd tarlltr) to tht saoplt 1n tht Soxhltt
thlmolt. Chargt tht Soxhltt with tolutnt and reflux for a ptrlod of
16 hours. After txtractlon. allow tht Soxhltt to cool, rtaovt tht
tolutnt txtract, and transftr 1t ta anothtr saaailt vassal. Concantratt
tht txtract to a voluoa of approxlmauly 40 m\ by using tht nltrogtn
blowdown apparatus dtscribtd aarlltr. Procatd with tht sanpla fractlona-
tlon and claanup proctdures dtscribtd btlow.
7. Proctdurts for Claanup and Fract1onat1on of Saoplt Lctncts
Tht following column chroma togrepMc samp It c1 tan-up procadures
are ustd 1n tht orttr glvtn, although not aVI may bt required. In
gtntrel, tht silica and alumina column proctdures are considered to bt a
minimum requlremtnt. Accaptablt alternatlvt claanup procadures may bt
ustd provldtd that thty are damonstrated to afftctlvtly transmit a
B-10
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representative set of the analytes of Interest. The column chnwato-
oraphlc procedures listed here have been demonstrated to be effective
fer a trfxture consisting of 1,2,3,4-TCDO. 2.3,7,8-TCOO. 2.3,«,8-TC2«,
U2.4.8-TCOF. 2.3,7.8-TCOF, 1,2.3,7,8-PeCOO, 1,2.4.7,8-PeCflF, 1.2.3,4,7,3-
HxCOO, 1,2.4,8,7.9-taCOF, 1,2,3.4,6,7,8-HpCOO, 1,2,3.4.6,8.9-HpCOF,
OCOO and OC8F
An extract obtained as described In the foregoing sections 1s
concentrated to a voluoe of about 1 eC using the nitrogen blowdown
apparatus, and this Is transferred quantitatively (with rinsings) to
the combination silica gel coluan described below.
7.1 Co*1nat1on S111ca Gel Colian: Pack one end of a glass
coluen (20 at. 0.0. x 230 HI In lenath) vltft glass wool (precleaned)
and add. In sequence, 1 g silica gel, 2 9 base-eod1f1ed silica gel,
1 g silica gel, 4 g ac1d-«od1f1ed sllfca gel. and 1 9 silica gel.
(Silica gel and aadlfled silica gel are prepared as described in the
Reagents sections of this protocol.) Preeluta the colon with 30 et
hexane and discard the eluate. Add the saeple extract 1n S et of hexane
to the collar along with two additional S el rinses, flute the colum
with an additional 90 et of hexane and retain the entire eluate.
Concentrate this solution to a voluoe of about 1 •!.
7.2 Basic Alumina Coluen: Cut off a 10 et disposable Pasteur
glass pipette at the 4 et graduation eark and pack the lower section with
glass wool (precleaned ) and 3 g of Woe IB basic aluerlna (prepared as
described 1n the Reagent section of this protocol). Transfer the
concentrated extract from the constitution silica coluati to the top of
the coluen and a lute tht coluen sequentially with 18 si of hexane,
10 «L of IX nethylene ch1or1de-1n-hexane and 15 H. of SOS eithylepe
ch1or1de-1n-hexane, discarding the first two eluate fractions and
retaining the third eluate fraction. Concentrate the latter fraction
to about 0.5 oL using tht nitrogen blowdown apparatus described earlier.
7.3 K-21 Carbon/Cellte 545 Colum: Take a 9 Inch dlsoosabU
Pasteur pipette and cut off a O.S Inch section froa tne constricted tip.
Insert a filter paper disk at the top of the tube, 2.5 ca. from the
constriction. Add a sufficient quantity of PX-21 Carbon/Cellte 54S
(Prepared as described 1n the reagent section of this protocol) to the
tube to fora a 2 CB. length of the Carbon-Cell to. Insert a glass wool
plug. Preeluta the coluen 1n sequence with 2 eL of SOS benzene-in-«tny1
acetate, 1 eL of SOS eethylene chlorlde-ln-cyclohexane ind 2 at. of hexane.
and discard these eluates. Load the extract (1n 1 wL of hexane) froa
the aluerina coluen onto the top of the coluan, alone, with 1 as. hexane
rinse. Cluta the coluan with 2 "L of SOS eathylene ch1or1de«1n-hexane
and 2 et of SOS benzene-In-ethyl acetate and discard these eluates.
Invert the coluen and reverse elute 1t with 4 rt. of toluene, retaining
this eluate. Concentrate the eluate and transfer 1t to a React 1-ml
for storage. Store extracts 1n a freezer, shielded fro* light, prior
B-ll
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to SC-HS analysis. If desired, still another column chroma tograoMc
clean-up step can bo employed prior to concentration of the extract,
as described below.
7.4 S1l1ca/01ol Micro Column Cleanup: After the above clean-up
steps small amounts of highly colored polar compounds nay be present In
complex samples. These are removed. If necessary, by the following
column: Push a smell plug of glass wool Into a disposable 6 me l.d.
flass Pasteur pipette, followed by 3 me of Sepralyte (Analytlchem
International), 6 m of silica gel and finally 3 em of sodium sulfate.
The column Is pre-wet with hexane, the sample Is applied 1n 100 ui of
100S hexane and eluted with hexane, collecting 1.5 el.
8. Procedure for Analysis of Sample Extracts for PCDO/PCDF Using Sas
Cnromatagraphy-mss Spectroaotry (tt-MS).
8.1 Sample extracts prepared by the procedures described 1n the
foregoing are analyzed by GC-MS utilizing the following Instrumental
parameters. Typically, 1 to 8 uL portions of the extract art Injected
Into the SC. Sample extracts art first analyzed using the 08-8 capillary
SC column to obtain data on the concentrations of total totra-through
octa-COOs and COfs, and on 2,3,7,8-TCCO. If tatra-OJFs are detected
In this analysis, then another aliquot of the sample 1s analyzed 1n
a separate run, using the 08-225 column to obtain data on the concentration
of 2.3.7,8-TCOF.
8.2 its Chromatograph
8.2.1 Injector: Configured for capillary column, sp11t1ess/sp11t
Injection (split flow on 60 seconds following Injection), injector
temperature, 2508C.
8.2.2 Carrier gas: Hydrogen, 30 1b head pressure.
8.2.3 Capillary Column 1: For total tetra- through octa • CSfls/COFs and
2,3,7,8-TCOO, 60 N x 0.25 me 1.0. fused silica 08-S; temperature pro-
grammed (see) Table 1 for temperature program). Capillary Column 2:
for 2.3,7.8-TCD? only, 60 M x 0.25 mi 1.0. fused silica 08-225, twenture
; for I «1n.. then Increase from 18Q«C to 2WC t S-C/«m.,
programmed
hold at 240*C for 1 «1n.)
8.2.4 Interface Temperature: 2SQ*C
8.3 Mass Spectrometer
8.3.1 Ion1zat1on Mode: Electron impact (70 eV)
-------
3 3.2 Static Resolution: 1:600 (10* valley) OP 1:10,000 depending
uBflfi requirements. Usually tht sample "tract* art Initially analyzed
uslne; low resolution MS, then 1f PCOO/PCOf art detected. It Is desirable
to analyze a second portion of the sample extract using high resolution
MS.
a.3.3 Source Temperature: 250°C
8.3.4 Ions Man1tared: Computer-Controlled Selected-Ion Monitoring,
Set Table 1 for 11st of Ion masses monitored and time Intarvals during
which Ions characteristic of each class of C80s and COFs art monitored.
1.4 Calibration Procedures:
1.4.1 Calibrating the MS Miss Seal*: Ptrfluoro Kerosene, decafluoro-
triphtnyl phosphlnt, or any othtr acc«pttd mass marker compound oust bt
Introduced 1nta tht MS, 1n ordtr to calibrate tnt nss scalt through at
iMit «/x 500. Tht procedures specified by tnt mnufacturtr for tnt
particular MS Instnmnt ustd art to bt twloytd for this purpost. Tht
nss calibration should bt rtchtcktd at least at I hr. operating intervals.
1.4.2 Tab!a 1 show tht tt tonperaturt proorasi typically used to
resolve each chlorinated class of PCOO and PC9F from the other chlorinated
classes, and Indicates the corresponding tint Intervals during which Ions
Indicative of each chlorinated class are monitored by the MS. This
toaperature program and Ion eonltorlng t1« cycle must be established by
each analyst for tht particular Instrumentation used by Injecting aliquot*
of Standard Mixtures C, 0. and I (See earlier section of this protocol
for description of these mixtures)• It nay bt necessary to adjust the
taaptrature program and 1on eonltorlng cycles slightly based on tht
observations from analysis of these elxtures.
8.4.3 Checking
-------
of tini Its ptrforaanct can also bo gauged by noting tht peak
t 1/2 Pt*k ha1«lit) fw 2,3,7,8-TCOO or for 2,3,7,8-TCOF. If
this peak width 1s observed to broadin .by 201 or tore as compared to
tht usual width for satisfactory optratlon, than th« column resolution
1s suspect and aist bt cheeked. If the colunt rtsolutlon Is found to
b« 1nsuff1c1tnt to resolve 2,3,7,8-TCOO and 2,3.7,8-TCOF froa thtlr
ntlghborfng TCOO and TC8F Isottrs, respectively, (as Measured on tat
t»a dlfftrtnt coluars used for resolving these two 1so*trs), then a
Of-5 and/or Of-225 SC coluen aust b« Installed.
1.4.4 Calibration of tht «-«-« systea to accomplish quantitative
analysis of 2,3,7,8-TCflO and 2,3.7,8-TCOF, and of tht total tatra-
through octa-COOs and C8Fs contained In the saaple extract,Is accoapllshed
by analyzing a sarlts of at Itast tnrtt wsrtlnq calibration standards.
Caen of thtso standards Is prtpartd ta contain tin saM concentration
of tacft of tnt stablt-lsotoplcally labtlltd Intarnal standards us«d
htrt (Standard Mlxturt A) but a dlfftrtnt concantratlon of natlvt
PCOO/PCOF (Standard Nlxturt C). Typically, «1x tarts will bt prtpartd
so that tht ratio of natlvt PCOO and PCOF to Isotapleallylabtlltd
PCOO and KOf will bt on tht ordtr of 0.1. Q.S and 1.0 In tht thrtt
working calibration rJxtarts. Tht actual ctnctntrations of bath natlvt
and Isotoplcallylabtntd PCOO and POP 1n tht working calibration
standards will bt stltcttd by tht analyst on tht basis of tht cancan*
tratlons to bt naasurtd 1n tha actual saopla txtrtcts. At tha tloa
wnan allquots of tach of tht standards art Injtcttd (and also whan
1njtct1ng allquots of actual saapla txtracts). 1f daslrtd, an aliquot
of a standard containing typically 1 n? of HCU-2,3,7,«-TCOO (Standard 8)
can bt drawn Into tha Micro syrlnga containing tnt calibration solution
dtscrlbtd abovt (or tht saapla txtract) and this Is than co-lnjtctad
along with tht saaolt txtract In ordtr to obtain data permitting
calculation of tha parcant rteavary of tht l*Cu-2,3,7,l-TC50 Intarnal
standard. Equations for calculating rtlatlvt rtsponst factors fro* tht
calibration data dtrlvtd frot) tht calibration standard analysts, and for
calculating tht rtcovtry of tha llCu-2,3,7,S-TCOO and tht othtr
1sotop1ca1lylafitlltd PCOO and POP. and tht conctntratlon of natlvt
PCOO and PCQF 1n tht saaola (from tha txtract analysis), art suonariztd
btlow. In ttitst calculations, as can bo sttn. 2,3.7,8-TCOO 1s tooloytd
as tht 1l1ustrat1vt aedal. Hovavar. tha calculations for tach of tht
othtr natlvt d1u1na and furtns 1n tht saoplo analyztd art accanpllshtd
In an analgous tannar. It should bt notad that In view of tha fact
that Staft1t-1sota01ca11y labelled Internal standards corresponding to
tach tttra- through octachlorfnattd class art not used here (owing
to llarftad availability at this t1a») tha following approach is **oottd:
For quantltatlon of tatrachlorlnatad dlbanzofurans uCi»-2.3,7.B-TCOF
Is usad as tht Intarnal standard. For quantltatlon of tatrachloro-
d1btnzo-p-d1ox1w, l>Ci»-2,3.7.«-TCOO 1s usad as tha Intarnal standard.
For quantltatlon of PtCOO, HxCOO, PtCOF, tnd- HxCOP, tht corresponding
stabla-lsotaplcally labtlltd HxCOO and HxCOF Internal standards art usad.
For quantltatlon of HpcOQ, OCOO, and HpCOP, OCDF, tha 1sotoo1cally
labtlltd OCOO and OCOF, respectively, art usad. Inherent 1n this
approach 1s tha Assumption that tha rtsponst factors for each of tht fsooers
8-14
-------
flf tach chlorinated class art tht samt, and in tht cast tf the ptnta-
Imi hcota-COOs and COFs, tht assumption 1s aadt that tht rtsponsts for
tntst CMO classts art tqulvaltnt to those for tftt tatra-1somtrs and tht
, rtsp«ct1vtly.
8.4.5 Equations for Calculating Rtsoonst Factors, Conctntntion of
2,3,7,5-TCCO In An Unknown Saoplt, and RtcovtHts of Intarnal Standards.
Equation 1: tasponst Factor (RR5) for natlvt 2,3.7.*-TCOO using
l'Cia-2,3t7,8-TCDO as an Intarnal standard.
•htrt: A, • SIM rtsponso for 2,3,7ta-TCM ton at «/x 320 * 322
A, • SIM rtspons« for "Cia-2,3,7,a-TCDO Inttmal standard
11 1on at a/z 332
C1s • Conctntntion of the Inttmal standard (pfl./ui.)
Cf • Conctntratlon of tht 2.3.7.KTCOO (p«./uL.)
Equation 2: Rtsponst Factor (W) forITC\ -2,3,7, 8-TCDO, tht co-1njtcttd
txttrnal standard
A4c • SIM rtsponst for llCli-2,3,7,8-TCDO Inttmal
11 standard 1on at «/z 332
AM • SIM rtspons* for co-lnjtcttd 1TC1,-2.3,7,8-TC30 txttrnal
n standard at «/Z 328 - O.OOf (SIM rtsponst for natlvt
2,3,7,«-TCaO at a/z 322)
C1s • Conctntratlon of tht Inttmal standard (p?./uL.)
Cts " Conctntntion of tht txttrnal standard (pg./ul.)
B-15
-------
Equation 3: Calculation of concentration of native 2.3,7,3-rCflO
llCii-2,3,7,S-TCDO 41 Intamal standard
Concentration, pa../g. • (A,) (I
where: Af • SI* response for 2.3,7,3-TCOO ion it a/z 320 * 322
Au • SIM response for the llCu-2,3,7,3-TCflO Internal
19 standard Ion at a/z 332
I, • Aaount of Internal standard added to each sample
M • Height of soil or «e*te In treat
• Relative response factor froa Equation 1
Equation 4: Calculation of I recovery of "^-2.3.7.3-100 Internal standard
S Recovery
A1s • SIM response for "Cia-2,3,7,3-TCDO 1«ternel standard
A • SIM response for ITCU-2,3,7,J-TCBO external standard
" Ion at a/z 321 • 0.009 (SIM Response for native
2,3,7.a-TCDO at a/z 322)
E. • Aceunt of "CU-2,3,7.1-TC80 txternal standard
co- Injected with saeale extract (nq.)
I. • Theoretical aeaunt of lJCii-2.3,7.J-TCBO Internal
standard 1n Injection
• Relative response factor froa Equation 2
As noted above, procedures s1>11ar to these are *pp11ed to calculate
analytical results for all of the other PC88/PC3F deterorined 1n this nethed.
I.S Criteria Which GC-m Data Must Satisfy for Identification of
PCOO/PCOr In Staples Analyzed and Additional Details of Calculation Procedurts,
In order to Identify specific PCOO/PCtf 1n satales analyzed, the
data ootalned must satisfy the following criteria:
I.S.I Mass spectril responses aust be observed tt both the Molecular
and fragment 1on Basses correspondlnf to the Ions Indicative of each
chlorinated class of PCOO/PCOF Identified (see Table 1) and Intensities
of these Ions aust aaxlalza essentially slaultaneously (within + 1
second). In addition, the chroaatoeraphlc retention fines observed for
each PCOO/PC8F slonal aust be correct relative to the appropriate
B-16
-------
a~ labelled Internal standard and oust be consistent
the retention time winder astablished for the ch1or1n«ted grouo to
which CM particular PCOO/PCOF is. assigned.
1.5.2 The ratio of the Intensity of the molecular 1on (ft)* signal
ta that of the (w»2)+ signal oust be within + 101 of the theoretically
expected ratio (for example, 0.77 In the case* of TCOO; therefore
the acceptable range for this ratio Is 0.42 to 0.92).
1.5.3 The Intensities of the 1on signals aro cons1d«r*d ta be
detectable If oach exceeds tho baseline noiso by a factor of at laast
3:1. Tnt 1on inttnsitlts aro considered to bo quantitatively noasurablt
If oacn Ion 1nt«ni1ty excoods tno basoHno noiso by a factor of at
lout 3:lc.
I.S.4 For rellaala dttactfon and quantltatlon of FCOT ft 1s also
dtslrafelo ta aonltor signals arising fro* chlorlnatad dlsnonyl othors
«n1div 1f prtsont could give rise ta fraomnt 1ont yielding Ion easses
Identical ta those ean1tared as Indicators of the PCOF. Accordingly,
1n Taale 1, appropriate chlorinated dlphenyl other aasses are specified
which wst be aanltared simultaneously with the PC8F 1on-«asses. Only
when the response for the dlphenyl tther 1on eiss Is not detected at
the sam t1oe as the PCS? 1on MSS can the signal obtained for an
apparent PCS? be considered unique.
I.S.S Measurement of the concentration of the cangeneri 1n a
chlarinatad class using the eathads described herein Is based on the
assumption that all of the congeners are Identical ta the calibration
standards employed in terms of their respective chemical and separation
properties and 1n terms of their respective gas chromatograpnic and oass
spectrometHc responses. Using these assumptions, for example, the
"Cti-2,3,7,8-TCSO Internal standard 1s utilized as the Internal
calibration standard for all of the 22 TCOO Isomtrs or congeners.
Furthermore, the concentration of the total TOO present 1n a sample
extract 1s determined by calculating, on the basis of the standard
procedure outlined above, the concentration of each TCOO Isomer peak
(or peaks for multiple TCOO Isemers. where these coelute) and these
Individual concentrations are subsequently summed ta obtain the concen-
tration of "total" TCOO.
c* In practice, the analyst can estimate the baseline noise by Measuring
the extension of the baseline Immediately prior ta each of the two aass
chromatographlc peaks attributed ta a given PCOO or PCOF. Spurious signals
nay arise either from electronic noise or from other organic compounds 1n
the extract. Since 1t may be desirable to evaluate the judgement of the
analyst 1n this respect, copies of original mass chrematograms must be
Included In the report of analytical results.
B-17
-------
8.6 Frequently, during the analysis of actual sample extracts.
extraneous compounds which art present In the extract (those organic
compounds not completely removed during the dun-up phase of tht analysis)
CM cause chances 1n the liquid and gas chromatographlc elutlon characteristics
of thai PCao/PCOF (typically retention tines for the PCOO/PCDF are prolongtd).
Such extraneous organic compounds, when Introduced into the mass spectro-
meter source My also result In a decrease In the sensitivity of the MS
because of suppression of 1on1at1on. and other affects such as charge
transfer phenomena. The shifts 1n chromatographlc retention tints are
usually general shifts, that 1s. the relative retention times for the
PCDO/PCOf are not changed, although the entire elutlon time scale 1s
prolonged. The analyst's Intervention In the «•« operating sequence
can correct for the lengthened GC retention times which are sometimes
observed due to the presence of extraneous organic* 1n the sample
extract. For example, using the prograai outlined 1n Table 1. 1f the
retention time observed for 2.3,7.8-TCOO (which normally 1s 19.S el nut as)
1s lengthened by 30 seconds or eon, appropriate adjustments 1n the
programing sequence outlined 1n Table 1 can be made, that Is, tach
selected Ion-monitoring prograai Is delayed by a length of time propor-
tionate to the lengthening of the retention tlavj for the 2.3,7,«-TCDO
Isoaeir. In the case of 1on1zat1on suppression, this phenomenon 1s
Inherently counteracted by the Internal standard approach. However.
1f loss of sensitivity due to 1on1zat1on suppression Is severe,
additional clean-up of the sample extract eay be required 1n order to
achieve the desired detection Halts.
9. Quality Assurance/Quality Control
9.1 Quality assurance and quality control are ensured by the following
provisions:
9.1.1 Each sample analyzed Is spiked with stable 1sotop1ca11y labelled
Internal standards, prior to extraction and analysis. Recoveries
obtained for each of these standards should typically be In the range
from 60-901. Since these coeoounds are used as tru* Internal standards
however, lower recoveries do not necessarily Invalidate the analytical
results for native rCOO/PCOF, but say result 1n higher detection Halts
then are desired.
9.1.2 Processing and analysis of at least one method blank sanple
1s accomplished for each set of saaples (a set being defined as 20 sasvjles
or less).
9.1.3 It 1s desirable to analyze at least one sample spiked with
representative native PCOO/PC8F for each set of 20 or fewer sanples. The
result of this analysis provides an Indication of the efficacy of the
entire analytical procedure. The results of this analysis will be
considered acceptable If the detected concentration of each of the native
B-13
-------
PCOO/PCDF addtd to tht sample 1$ within +501 of tht known concentration.
(An approprlatt stt of natlvt isomtrs to bt addtd htrt 1s a stt such
as that Indicated for Standard Mxturt C.)
9.1.4 At lust ont of the sanplts analyzed out of tich stt (of 20
samples or less) 1s analyztd In duplicit* and the results of tht duplicate
analysis art Included 1n tht rtport of data.
f.l.S Nrforwnct tvaluatlon saoplts prepare* by CPA,or other
laboratories, which contain representative POffl/PCOF In conctntntlons
approximtinf thest prtsant In typical fltld sa^lts btlng analyztd
(but unknown to tht tnalyzln^ lab) should bt ptrlodlcally dlstrlbuttd
to laboratorlts aecoopllshlng thtst analysts.
9.1.6 Sourets of all calibration and ptrfornanct standards ustd 1n tht
analysts and tht purity of thtst nattrlals sust bt sptclfltd in tht dau
rtport.
10. Data Rtportlno.
10.1 Each rtport of analysts accomplished uslno tht protocol
dtserlbtd ntrtln will typically Includt tablts of rtsults which Includt
tht following:
10.1.1 Ccoplttt 1dtnt1f1cat1on of tht saapl«s anal/ltd (sampIt
nuMbtrs and sourct).
10.1.2 T)it datts and tints at which all analysts wtr* accasnpHshtd.
This Information should also appoar on tach oass chronatofram Includtd
with tht rtport.
10.1.3 Raw rnss chromto^raphlc data which consists of tht absoiutt
Inttnsltlts (bastd on tlthtr pttJi htlfht or ptak arta) of tht signals
obstnrttf for tht lonnaissos oonltortd (Stt Tablt 1).
10.1.4 Tht calculated ratios of tht 1ntans1t1ts of tht ooltcular
Ions for all PC90/PCOF dottcttd.
10.1.S Tht calculated concentrations of native 2,3,7,8-TCOQ and
2,3,7,I-TO3F, and tht total concentrations of tht congener* of each
class of PCBO/PCOF for each saaplt analyztd, txprtsstd In nanograos
TCOO per grast of saoplt (that 1s, parts-ptr-b11l1on) as determined
freti tht rt« data. If no PC80/PCOF art detected, tht notation "Not
Detected" or •ft.O." 1s ustd, and tht aUnlauei dtttctablt concentrations
B-19
-------
(or dtttctlon limits) art rtportad.
10.1.6 Tht sana raw and calculattd data which art provided for tht
actual saaplts will also bt rtportad for tht dupllcatt analysts, tht
•tthod blank analysts, tht spUtd samp It analysts and any othtr QA
or ptrfomanct saaplts analyztd in conjunction with tht actual samplt
stt(s).
10.1.7 Tht rtcevtHts of tht Internal standards 1n ptrctnt.
10.1.a Tht rtcovtHts of tht natlvt KOO/PC&F froa splktd sanplts
1n ptrctnt.
10.1.9 Tht calibration data. Including rtsptnst factors calculated
froa tht thrtt point calibration proctdurt dtscrlbtd tlstwhtrt In this
protocol. Data showing that thtst factors navt bttn vtrifltd at Itast
ones during tach S hour ptHod of optratlon or with each stpante stt
of saaplts analyztd oust bt Includtd.
10.1.10 Tht wtlght or quantity of tht original saaplt analyztd.
10.1.11 Oocuntntatlon of tht sourct of all ?COO/PCCF standards
ustd and avallablt sptclflcations on purity.
10.1.12 In addition ta tht tab1«s dtscrlbtd abovt, each rtpert of
analysts will Includt all BBSS chroaatograas obtalntd for all saaplts
analyztd, as wtll as for all calibration, SC coluan ptrforatnct, and
SC "window" definition runs and rtsults of caluan ptrforaanct chtcis.
10.1.13 Any dtvlatlons froa tht procadurts dtscrlbtd In this protocal
which art appHtd In tht analysts of saoplts will bt docuatnttd 1n
dttall in tht analytical rtport.
11. Typical Data Ind1cat1vt of Mtthtd Ptrformnct - Prtc1s1on and Accuracy.
11.1 Tht Mthtd dtscrlbtd htrtln has typically bttn wploytd ta
quantltatlvtly dtttnrtnt 2,3.7,1-TCOO 1n eotaiiiitlon product sa«Dlts at
conctntratlons as low as 10 p1cograas/gna and as high at 100 u«/g.
Canctntratlons of tht othtr PCOO/PC8T which can bt dtttcttd typically
fall within tht rangt of 20 pIcsgraBf/lsowr/graii of samplt, ta 100
p1cograns/g of saaplt. Of count, tht Halts of dtttctlon which can
bt practically achltvtd art dtptndtnt on tnt quantity of saaijlt avallablt
B-20
-------
tftt atwnt and kind of otfttr 1nttrferr1ng organic rtsldues which art
prtstnt in tftt saaple. «1tft rtsptct to precision, tftt avtragt dtv<«t1on
of data ofttaintd from tftt analysts of a nuafetr of aliquot* of tftt sam
saavlt containing tftt 2.3,7,3-TOO Isontr In tftt 250-300 ppb rangt
Is tstlntttd to bt +101 or bttttr. Data on tftt precision of quantltatlon
of miltlple PC30/PCBF In a ilngle saaplt art not as ytt avallablt. As
v«t, tfttrt Is Inadequate Inttrlabtratory and ptrfomnct evaluation data
available to sotclfy tftt accuracy wftlcft can bt expected of tftt analytical
procedures dtscHbtd *—*<-
B-21
-------
it *
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3 II
1
s. s.
s. s.
5
ill
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.
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-------
APPENDIX C
ANALYTICAL METHODS FOR PCBs
-------
Netted «M. OocacBiaMioa at Moclcidoo «ad
la V««o* and Soil/9
by «»• c&rojM
1M3
•.
VUUJHI U
9. 1. lavlxaaBMical rroc««clo«
da«laa«cX» Ohio 4S2<«
C-l
-------
1
2
3
4
S
9
10
11
12
13
14
19 Nafa
«aa Z4aa«i£ica«iaa
1 t*i«a»i>ili< «C
2 KB Caaaaaaxa Oa«4 aa Cilibraaiaa scaoaaxaa
3 Irtaaa far fvaaaratiaa af Id Staa* Salaclo*
4 ?«paaiUua «a4 Appraalmca Caaaanracioaa of Cali&ratiaa Soiatioa*
far PttOI-Raafa Oa«a Aeajm«ldaa
$* i"i-»p«Lraua «a4 AppraAaava C0a«aa«racioaa a< Calibration Solaslana
A* &N Oa«a fcaa^l ittiaa ter Kl Oa«araxaadaa«
A Ciapuaicia* aa4 A*prwalaa*a Caa«aa«racioaa ot
flar SXH Oa«a A«a«lclaa far
ter
7* Zaaa tor Salaata* Zaa namiaariaa; ca Oataaiaa KBa &r
Oat* tor raw Sata af <3S Zaaa taam
7b Zaaa tor SalaataA Zaa namiaanjw «a
••»« Zaa Sata af <*9 Zaaa Caa« tor SalMtaA Zaa
!taa Oata far KB Zjaaar Qraaaa «a4 Calibratioa Coaaaaara
tor ialaacaa Zam NaaXtarla* Oar- Aaa^iaitiaa tor »aa«iaida
Kl Aaalyvaa, Zataraal staaaaraa. tmA Sarraamta Ciaiaanaila
f T»tiaaUam tor Zatarfaraaaa af KB ruaiiUliif Twa M41tiaaal OUariaaa
14 Carraamiam tor Zatarf araaaa af KB Gamtaiaiav Oma Mattianal Oilartaa
^ *aaa«aar a»4 fvaalaiam af Atttaaataa Haaamramaata af KBa aa4 raatieidac
la rarvifiai watar
laa eorraac praflla of KB caJ4£ratiaa eaaaaaan aad
Aaalytaa
Olaavam laflicatiAv tpprasiaata ralativa rataatloa daaa of KB
C-2
-------
1. scan AMD
1.1. ttU Mttod provido* proeadurM for MM spcctraMcrie aoearainatioa
otf polrc&lonaac** blaJMayla (KB*) aad th« U*«*4 panlcidM IA *«
•oil, or loittBBM. Thi* M«te4 tJ apyUeabU to MM*!** eoacalalav
or M «aBpl«B •ixcorva, «udi u co*Mr«l«l Aroelon
for
e12ltCl« 309-40-2
319^4-4
319-4S-7
S103-71-4
C19A>C1« S 103-74-2
397«5-«0-S
72-93-4
30-29-3
«o-f7- 1
939-M-O
33213-43-9
1031-47-0
73-20-0
Ct}l«CL«0 7421-93-4
33494-70-5
1024-57-J
73-43-9
27323-10-0
23312-42-9
23323-40-4
20914-33-4
29431-29-2
20401-44-9
210JS-71-2
31471-03-0
33743-07-7
2031-24-3
C-3
-------
1.2 Oacaoxioa Ualta vary 4aaa* aacaod aaalytaa »ad vita aaayla aacrix, saapla
atloa procadoraa* condition of caa GC/W rrataa* cypa of data
u «ad iadividoal aaarplaa. taa cilmUtad aaeted data«*ioa
Uait (MR.) far aaea paaticida ia farelflad raaoaac vatar oxcraeta aaalTxad
vita full-raaoa data aeajoiaitiea la praaaotad la 3a«t. 14. Aaalyaia of
oaU&ratioa aalaxiaaa ^adioatad caat tlh^t oalcnlatad (B^a *1ir aot accarataly
faflaat iaatxtawatal dataajtioa Ua&ta* ^ha folloviav vvidaaca la baaad oa
at eallBra«iom aalotioaa vita oaa iaatraaat ovar 4 pariod
aaaft. Wita aalaetad lea aaajtariaa (3X8) data aafataitiam* paa«ieida
aaalyta datacaioa Uaita 4ra lovarod by a« laaat a factor of flra. Oataetiaa
\, vita caa dataotioa, Uao,« far liaitadilarnaipaaayl baia«
$•10 tia*a ^*T^*^T caaa caat. of a aaroxrhl umblithaiiyl • K aoaocteloro"
itaiaa 1 a« 4&d C«U-raaja« data ara
LLait far total 9da vill dapaad oa caa
ia*. sat data 4*ajaiaiti0a pracaavraa cadoca caa datactioa
Uait far fda by at laaa« a faotar of earaa.
2.
A 1-t ««car aaapla ia aiaaaA ia a aaparatary ffoamal 4aa* awcraccad wt«n •a«aylaaa
calarida* &epra*«ia«a aitraeviaa araoadaraa far aail/aatfiaaoc saa*)JLaa will ba
•44*4 «a«a ravalsa *r« ntnri1na< froB aaaalaf aapariaaa«a. tlia axcaraes la dA»d
4a4 aacaiaaail ea baaaaa avria* eoaeaasra«lea «a 4 fiaal waluaH) at 1 ad ar laaa.
Saopla «rtra«« «aaaa«aa«a ara aaaarsvaA vita aaaiHary «altaa> ama caraamcaaraptty
(QC) 4a4 14aafi£iaA aaa> aaaaiaraA vita lav raaalot-lM* alaavraa laaji^atiav aaaa
•paauiaam-j (W). Aa latatCaaaA data «r*«aa (09) ea aaatral data 4eqoi«iciea
aad ca saara* ravriava, 4ad aaalpalata aaaa taa«tral data ia aaaa*cial. Cis&ar
full-«aa«a ar »alaa«aa>»iaa aaalcartnf (SXll) data 4ra ii»pai'ad, dapaaiii
eaaaaatraviaa raaaai af eaaaan* X£ ffaU-raaav data ara aaipilrad, 4ll
aaalr««« caa ba IdaatXfiad aa* aa«a«rad vita OM Oe/M 4aalr*i** — «11 p«a«X-
eidaa 4a4 fda aavt ba datasalaaA *a4 if sat data «ra
da«ae«iaa Uai«a* ev« QC/W 4aalr««* 4ra aacaaaary, aaa ca dacaat aad aaaavra
a«aadarda«
bafara QC/W
ia«. All paa«icidaa
• raapaaaa of aaaa «avpaam>4 w tte W laapaaaa of caa iatanal
vita 4C raiaaiHa tla« aaarar that of tte paatiaida 4««lyta. T&a
I aaaa)la oaajtaaAaatiaa vita taaasiaal oalardaaa la ladiaatad by Idaat^i*
fl«atlaa aad aaaaaraaaat of cte tw« aaat panirtaax oja»aaanta» jaaaia-rtilardana
«ad naaaealar. (Xlpaa-«alardaaa aa4 Boptaaalar< otter aajor caaeoaaa«a of
caoftaieal Alordaaa* aay 4laa ba praaaax 4ad vill ba
caia aataad.)
•da ara UaatXflad 4ad aaaatarad aa laaawr froaya (!.«., by la^al of chlarioaeion).
& ceaaaacxatiaai ia aaaa«ra« far aaaa fd tauaair 9*0091 total Pd ooaeaacration
la aaoa aaaipla axtraot la obtaiaad by maaUat iaaawr aroap ooacaatrationa.
C-4
-------
ira aro oaod aa calibration fftaadarda. aad oao iatoraal
•taadard, cftryaoao"*^, la oaod to eaUarata M roapoaao ee VCBa, vUaoa aaaplo
Ltloa* rorolro tao oao at tao aocoad iataraal •taadard, phonanthraao-di a.
3.1 coneamaaxcm catmuno aotarzev (cat) — A aaia*iaa of aotao* aaaiytao
ta oaJOferaca tao MM •powi-naaior roapoaaa.
3.2 O3WUU Maon — T&Tna^teoat. cftia aatted* latflTtdaal KM* «r« da«erlb«d
Miafcar «Mi9i«« br »«U««tal«w aaA S«li (2). (thl* auabtf t»
to da«orib« ffO eaa««a«n la eataloyt yvotemd &y Oltra Sciantiiic,
I, XT.)
3.3 CfSZNUU. TPMPMC — A p«r« manual add«d «a « Mupla «RTMC ta taown
oehar eaapeuada
b« «
3.4 UMUSQKT OOfUSJ&tt (101 aad\ LS2) •*^*a saMBvla aLl^oava *ih^n la
vie* lrta««i«aA jgoaaAuraa.
daaltca«aa Ia41ea«aa gradalaa iaaa«l«tad vita laboratory
or rtara^w srocodacaa.
3.3 UJOXA7QXT 7SXTOMMKZ OXOC SOL07XOM (UC) — * aoltzftioa of avehed aaalr«M,
•utiu^ca eoapoiiaiia, aad lacanal naadaxda oaod ta rrmluata ta« pcr^oraaae*
of tto
-------
3.10 mammae* trnxaaza* SM9U — A aaaal* coairatnln? IOMWI eaaeaatratloaa
of aa«a»d aaalre** taac haa b««a aaalyxad *f auleipia Ul»ora«erlaa to
teeaaddM reattaticaily taa aceancy aad praeiaioa that eaa ba «xpac«ad
vnaa « aaeaed la 9«x«oxMd br * ccapacaa* aaalyat. Aaalr*« eoaca0«raciona
eo taa
3.11 QOXtrrr conraot (QC)
aC taa QC
taa aaalyaia la
ta a aaa»la aliqaat bacora artsaetAaa aad la aaaaorad wtca taa
raa uad ta aaaaoca •«•»!• eaaaaaaata. Aaaactatad wlta
ita caaaaaad *ra twa valaaa* laaarmcary aarraaata
(UD aad latooratarr awroaata aalka • taaavatxeai
tt a aorraaata eaaaaaad la oa aaaltar aatnad parfai
aaia.
4.
sSS.
4.1 Xa«acfar«aaa« aay ba OMaa4 by eaac«Blaaaca ia wlv«a«a.
aad oc&ar aaapia pro««Mla« a^aXaaaac* Labacacary raaaww blaaJca (UBa)
a«a aaalysa* ravciaaly ta daaaiM«rae« tiia« taaaa aacarlala ar« Sr«a o<
lataxfavaaeaa waar taa aaalytloa^ eaadlelaaa «aa4 few
4.3 90 alalaKa lacartaraaaaa* flaaavara (Ualaalaf aaaaia baetlaa)
ba aaxXcBloaalr claaaa*. JU aaaa aa aaaalAla af«ar oaa, rlaaa fUa«var«
«1«A cfta laa« aal^aa« «aaa» tSiam «aaa «l«ft aaM»aaa» la hat xatar aaa
riaaa «tta taa «a«a* «aUawa« by
-------
-01 —
»T »•*» «*T»«P
*9&O9A0ftl
*»oi m DO*
9»-OOC — HMT4
••WTi >•••! V»^»
fft
»*ft
mrr* ••
•w nsrn »T«
W*» OS • «l X
t*r*»
"3-t —
r*t*t
rr
xo i-i (ff
on
V *pecR( *
"7
1*5
-------
4.3 (JOHWMJttZSD (SC/MB STTTJEM
4.3.t tno «C mre bo capaalo of toaporaeoro prooraaBiaa aad bo
wica All roajoirod accaaaoriaa, such aa •yriaoaa. oaaaa, aad «
colua*. Tao QC iajoeeioa pore aaatt bo oaaioaod for capillary eoluana.
Kaaaal tplitlaaa iajocelaaa war* oaod to aeajoir* daea uaod aa cao baai«
Cor ojaality eostrol roo^lxoaoaca. Aa aacoaa«ie lajoceor, oevovor, la
it •haald pvovtda lor* praoLM r««aaclea «!••• &ad
alnlatta* wtca tau r«rti«t«n«. vt«a MB
of tlM lav t«ift«l HBTiiaa taavaracara r«^oir«d for
will caoa« 1rr^prneaa ra««
or fi-r*
far «*«a a«aXtar«4 toa walla « saapla «a«faa«a« «lue««
from tte «C« TSio M mart prodam * a«aa rpaccroa a*««la* til cris«ri»
for <20 af of aMafluerovrlaaoarlplMavalaa (OfTT*) iavroaoaod titrauo*
QC
BOB (OS) i4 roajolrod ca acajolro, rcaro,
spoocral dmca. taa Of amre bo capaalo of
a daca fllo far rpao^fla iaaa aad placdav iaa aooAdaaaoa
or •paocna rniahor ca pradwra «olo«tod ioa otrroa« profllao (StCT«)
aad oauautad ioa carroa* profilao (XXCM). AUa roa^irod i« cao
or •paouoa aoaa«ra la StOa or CXOa. tcmal dmea aeo^ijizioa
4.3.4 CK Op«iaa — for S&t daca aaa^iAitiaa. caa Of aaa« bo o««i9pod
oapaalo of aea^iriaa; da«a for anl&ipla oroopa of iaaa.
• ama« allow a««aam«ad aad rapid caaaooa of cao soc of iona
iltavod* To aoa^lro all m daca aaodad far taploaoncauion
Lf-iTaUaala avcaataaad ia«arpro«a«ioa proaoduroo. caa
daca far fear oraapa (or
i> oaaa ooaalaciaa? of jt)>9 iaaa or far fiva fvaapa of <,20
k« flM c^Aaa apaa>c aaalcarlaor iaaa dodao^ aaaipla aaalyooa
eallaraciam aalacioaa war*
4.4 OC OStOMI — * 30 a X 8.32 mm SB fmaaA sllloa capillary aoloam eoavaa
a 0.25 « or thlokar tUrn croaaUafcod paaayl aacttyl ailiaoao daca aa
Dttrapoaa-i (D»-«), J aaa W Scloaelfia, lUacfta Cordova. A) or polyaiphoayl.
riayl diavcayl silMaua (sacft aa «-«4, Ulto«h Aaao«ia«oa, Ooorfiold. ri)
i« ro^xiroa. Oporaciav caaaltieaa loioim ca prodaeo aoeop«atolo r««ulsj WXCA
caoM coloaaa ar* *hawm La Taalo 1? •opara«iaa of pooxieida aaaly«oa aad 9C1
eallaraciaa canovaon wica a OB*9 eolujai aad eaooo oporacia^ condieiona i*
shown ia Fivoxo 1. to«oa«ioa tiaao na*o boon r«pore*4 (4) for all 20* PCI
C-8
-------
6-0
• I
»*•*•*
i'i
•*9 Ana ••pnp**»t
01
tea «•<»• p*8TT*oot7*» • VST* •T%**9 ««q*t n V?
« ooi
ye A tt't •**»»TO —
?»
tw ntnotiicp am
•» 1000*0
i»»a 90
* •*
aej
-------
7<9 VCB RXSBTIUB JIJJ1E (JUNUMKM fOK SZM OATX Afc^vi 13 A SIOT QPTXCtt — Kaevlad
of taa rataa«loa tiaaa of cartala conoaaara la nairaaaary to dataraiaa
vaaa eo aea^lra data wita «aatt ion avt* TMO caaeaatration callbratloa
eoaoaaara alao aarv* aa rataacxo* tlaw caaqaaarat taa 8ir*t alutia?
d1-»Cl ttrltrt*** taa tla* wfcaa data aeajolaltloa aoax ha»« ba«a
for loa M« H, aad tta dto-Kl iaalcata* «da« all »da acv« alu«*4.
oea«* to* M«a (S«c«. 9.4)
7.10
7.10.1 y«a«lelda Stack Solocioaa — rrapam £ro« ptva rcaadard aa«aviala.
apyroxlamtaiy 25.0 a* (wt«h «eeora«y of 0.1 *f) of cacti
tea empauad aarf «a«& pura paa«l«lda aaaly«a« axeaae
Caa X aa4 Kadoa«l£aa XX. for thoao swa paveleidaa* arapara
a no«k aala&laa e»lc« aa ceae«a«ra«a4 aa s&ac prapaxad Jar ocitar
potftXelda aaaly«aa. Oijavlw aaaft uuapaiiaJ la Itaaaa* aatf dlloea ta
wlam la a 10-«L (S-aC. for t&a am rtHnatilfitia) valumule 21aak.
(Caaoaacra«loa at aaaH aavavnaat • 2.3 aa/ab. asaapc Xndoaol^aaa,
vkiaH ateold ba S aa/aC.) Saallav «r larfar valuava a( reoek
aay »a oaa4 ti aaaicoA. If «ava««B4 pwltr la «arei£la4 a
caa welaat saa ba oaa* wteft*«« garrooloa «a ealeulaca sfta concan-
caa ««ock «eaaaju4 aola«la«. CaaBareiallr praparad
la ha«aaa eaa ba aaad at aay caaeaaezaclan li s
ara traeaaala ta Q9OA-«appl^«d «taad«rda.
7.10.2 Paatlaida Pria«rr Otlotlea Salocloaa — I eaoranlaas apprc
•alotaoa praparatlaa la to prapaxa tMa paatleida priawry diloclaa
aaloclaaa taat ara onaa taa aanaaaayatlaa a< tha 41«*aa< eoaeaatrat^aa
callaratloa aalocXam raa^lrad. taaaa aalocloaa aaa tftaa ba dilixead
praaara all aaadad oallbratloa aaUtclatta. Ona aa
alaaayda aad oaa «a«a aa«« bacaaaa t&a aadi
calxbratlam avlatloa doa« a«t oaatAia aadrla aldaayda. ?Uca 1 at.
of aaaa paatialda aaalyta/swraawta aaataoqad «ta«ft aelatlaa la *
23-«C. laliiaarrln flaak. (?a«al «alaaw ear all 22 paatielda aaalyvaa
aad 2 aminaata mamuuaaa • 24 ad.) iUka ta ivloa* «ltft baxaaa aad
wall* (CoMamxacla* of aidaanlfaa »afa«a» aodaamlfaa X aad
XX • 200 H"t/iii tmfitwt^^1
-------
vita taa taallaat paaaiala «o
haartapaca» and loaning vlala ahoold b« -itn1alT«i1.
7.11.2 KB Prlaary Dilation Standard — Taka aU*aa«a o* taa scoc*
•alacloaa of taa aiaa KB oaaeaatratioa calibraeioa cea«aaara tad
mi* tnfathar ia taa proparcloaa of oaa part of aaea aalatioa of tha
d, (»1), Gj («), 4»d C13 (»») nanaaaan, CM pare* of aaeH aolutAc
of taa a4 (MO), 0* (M7), aad O« (»1S4) eaa^aaan. tteaa parta
a« aaaft •loftlav-oC tte a? (*1M) and Oa (*200) oaa^aaara, aad fi-rt
taa dig (»20») Baatiaar aalatla*. (Vocat Tha rwtaatloa
daaaritowl la Sa«c. 7.9 aca aoj laaXadad ia tha KB
•aaaa ttttay «ra aoc n«dad for fail-ran?*
data aa^alaieiam.) TlUa will prvrlda a prlaaxr dilatXaa •caadard
wlocioa «< taa anapaaAUoa sbawa la TaAla 3. CaleoLata t&a eoaeaa-
tcaciom ia ««/uL« «aa tftraa •i9atffiaaa« Clfvaa. FUea aaeft tolation
ia a alaaa fiaaa vtal with a ?aflo*-Ila«a acrav eay aad rtara at
4«C. Mask taa aaaiama «a taa rial wall t» aaaitar aalmiaa
dvlav •vca^ar wloclaaa ara natola InaaftnUtaly l£ Mlrvat cra
ratiaa ia prvwatad.
w (Ctta).
7.12.1 a aalotion »1 (far fuli-raa«a QX*1 — «aiaa 7.S ay • 0.1 a*
- - • • • - ayyioaa-dt2» dlaaalva ia haxaaa and
i 10 aL ia a *»lnaa».rle flua. (Coaaaatratloa of
750
7.12.2 a Mloaiaa »2 (far SZM OkU) — Taka 1 tf. at 3 Mlnclaa »1 «ad
dllsaa u 10 ib ia a wlaaavrla flaak. (Caataatyatlaa «t «aca
a • 73 a*/*b>
wlotiaaa ara
iadiTidval
da
7.13 CU4 POlt FQUHUKI QaXJl
aa. taa aiaa K| aallkra
aad
v»a ia Taala 4.)
aa, ba«a •
aa ia CMC*
taa« allow ia)a««iaaa a<
evvrlaadiaf
i.)
(Hl«h OIL) ara praaaa« «e
wltbavt n saturation
7.13.1 Tha. r«U*Kaafa m«a Ctt eaa ba prayarad bf aftxlaa1 «^aal pertlona
o< taa KB prlaary dllatlaa Mlotla* aa4 tto paaxleida prlaarr
dtlatlaa Mlualoa taa« coatalaa vadsla aldakqrd* aad than addia* *a
•pproprlata f«luaa *t a salociaa *i. For inaafli, 1 at. of «aea
C-ll
-------
priaarr dUatlaa •oloeloa aad 20 oC, oC Si Mlaeiaa «1 proved* «h«
•aproariata caaeaaearacloa Cor Kloa CM..
7.13.2 Oe&ar full-raafa OtU ara pr*par«d by dllueiaw; eha priaary «ilu«Aoa
reaadard joiatiaaa aad addtaa; efca aapropriaea aaauae of IS M
• 1. OUKXOHt «w paaeiclda prlaacT dHatioa standard that, ra«aa«4,aa elaa oaaoaaari.
eba« ara taaad ea oataJiUali rrandieiaaa tor SIM data
7. ij rr«aar« a wloelaa of twrajata a»fi»ai1t la a «a«ar alacidl*
m fvovtaa a eaaaaavaciaa la eba aaaaia/blaak ««cra«c «ha« U aaar
tr»tlnn aa«l«laaead far aaalr*** **«*« *• *!!**•* «f >20 o& La
ca taa aaavla ba
t.l WOOL UKVUB
1.1.1 saapiaa aoac ba «allacBad la claaa (««««. 4.2) flaaa caacalaara.
•aaat «aa laapln aca aaclalaaaad ca caacala law caa«aacxa«loaa
ttf aaihad aaaiftaa* a aaapla lar^ar cbaa i-t aay ba naadad. Aa
yvaa la ca add a parvlaa a( anraavlav aal««a< ea
am ayf*oarla«a atl^ta* «*iua» U ayamaAaauaiT 1
-------
0.1.3 SaaaUaa sheuld ba octractad withla 7 daya aftar eolla«tioa aad aaalyvad
wltala 40 daya altar extraction.
0.2 SOIL/SID OUST SM7LXS — Approprlata pracaduraa will ba spacifiad whaa
raavlta ara oataiaad froa aa^elaf
Oaa»aatratlaa aad daaaamtatiaa ot aaaaptaala j til rial calibration la raojwLrad
baxara aay laaplaa ara aaalytad aad la raajolrad lataraittaatly threaonaut
aaayla aaalyaaa aa dioeatad by raaulta ot eaaclavlaa; caXLbratloa diaeka.
t» raajoirad at tha baqiaala* aad aad ot aach I2«a pariad dariav whieh
ara partamad. ma Naditaa CUa far paaeloida datasaiaatiaaa da net
aldahyda. tola allawa tha Itadloa GO. ta ba oaad far
«ka, Ualadtaa; a chaeft ta •aatara that aadria ijaouapui
. taitial eallbratiaa a laaarata Nadloa OS. eoatalalaa '
aad tha lataraal ataadard la aaalyaad ta dataxatfjM tha raaoaaaa factor
(a* aadxia Udaiqrda. f!iaraa» aalatlaa and
a aaaa aaaaama taa« iaaladaa data far a/a 43-430. u tha
Mt all aritaria (Taala •), tha « aaat ba
•M< all aritaria ba£ara prmraadiaa' with
9.2.3 FiUHIaaaa CaUteatlaa — Za)a«t a t- or 2-«t itlip«^ ot taa iiadlaa
CK aad aaajpira data fxaa a/s 4J ta 910. AaajHra >9 spactra doriaa;
^ gi «C aaaa. Tatal «yala tlaa aaamld ba >0.9 a aad fl.S •
^1.S a. *
CMTTXOMt Miaa aaa^iriaf SZN data. «C aaaratia^ eonUelaaa aoat ba
earatfolly rapredaaad tot «a«h aaalyaia ta prortda raoredoeidla
r«taa«laa tlawar Lt not, iaaa will aot ba aeaXtarad at uia
C-13
-------
9.2.4.1 sat Calioratioa for TCJ) daearaiaatioaa
9.2.4.1.1 TV« optlaaa far 3ZM data acejoiaitiaa ara provided.
Data caa ba acquired vita four *ata of f K> aaaoaaar *104, taa firrt
Stay aaajviaitiaa vith Zaa tot »2 aad bo^ia
Laa vith Zaa tot »3 Jnat (approxlaatalr 10 •)
ttiaa of TCI
_
C14-TC>. Stay ao^alaieiaa wiea Zaa S«« *3 aad aayla
a fl«« M )vae ( aasroi^aa«aly 10 i)
, 2-4,4'-OOT.
9.2.4.1.4 9ai d»«a iB^tUltiaa with tivt laa s««a.
omta wtta OM fawr Zaa S«ca 4aaarlb«d la s««s.
9.2.4.1.3 aad add a flfcH taa S«« b^iaala* data
lsa «aa« M« )ua« ( lafcnwl M«iy 10
•Imlaa «* TCI eeaaaaar *20«, U* iirre
CL^
9.2.4.2 SZH Caliaratiaa tar 7«a«ieiao 0««axBiaa«iaaa — Tir««
^19 iaaa aaeJi ar« oaod (Taalaa 9*10). t«tla data
Zaa tot »i bafar* «iation of alaaa-nc. tJu
of aldria aad bafam alotiaa of haptaaftlar oaoada.
aa^aiaitiaa vith Zaa tot *2 aad Turin aeajaiaitiaa vith Zaa
•3 afta* aiatiaa of aadaavlfaa ZZ aad bafara 4,4'«OOO.
9.2.5.1 r«U-«aaaa Oa«a
Aaaiyaia of Nadloa OU,
9.2.S.1.1 «C paifaiaiaaa — aaaaUaa ••aaradaa of b««a-MC
aad •maawOC; baaaliaa •aparaclaa of aadrla kacana
aad c*arr««»«"»i2t Baiaft« of ClfTCB paak ^«0% s«ca«9MC
paak hoioBCt hoiaa* of earyaaao-d^ P*** i*0% °< ^*
paak haiob* of aacaaxrealar, walea aay partially co«lus«
taa ClfKS
9.2.3.1.2 HI aanaitlrtcy — Siomal/aaiaa ratio of >9 far
a/* 499 of KB eoao^aor »209, C110-K3). *
C-14
-------
M calibration — Aboadaaca of £40% aad <60% of
a/s S02 ralatlra to a/s 499 tot tea conMnar »209.
9.2.5.1.4 Lack of 4o«radatloa of aadria. "••-Ini aa axtractad
loa earraat profUa (KCT) Cor a/s i7 la too rataatloa
boewaaa 4,4'-OO* aad aadaaulfaa solfatof
taat taa aboadaaea of a/i €7 a« tha rataatloa
aadrla aldaayda la <10% of taa tttMn-ian-t of
a/i «7 groiaurt br •adxla.
9.2.5.1.5 Lack of dacracaftLaa of 13C12-4,4'-OOT. teaalaa t!C?«
a/s 25* aad a/s 247 la taa rmaa«ioa Uaa window
eaat lacladaa 4,4'-OCO, 4.4'«OOC aaa 4,4'-oot> a/s
2St woald ba pvocoeaa by 13C12-4,4'00«, aad a/s 247 by
C12-4,4'-OOO. Caaflza tha« taa totai aboadaaca of
boca laaa U ,S for a/s
49» of KB oanvaaar «209, d19-»d, aad Tor a/s 241
9.2.5.2.3 MS calibration — Xbondanca of £79% aad <99« of a/s
500 raUtiTa ea a/s 490 far coa^anar »209, Ci1Q-fC3.
9.2.5.3 SSI feasiciat Data
9.2.5*3.1 OC •oyantioa — iaaallaa saaaratloa of aadria
feataa* aad aaryaaaa-a^t baaaUaa ••oaratioa of
•UC; baaallaa aoaaracloa of aadria
jf aaicM of ettrysaao i^c
>40% of •ochaayiimor paak aaloa*.
9.2.5.3.2 tt* aoaaitlritr — Sloaal/aolaa ratio of >S for a/s
241 of atey»aa«-d«2.
9.2.5.3.3 M oallbratloa — Abvadaaco of a/s 241
t» taa« of a/s 240 pvocacod by Garr»«ao-*i2 U >1S%
aad 05%.
9.2.5.3.4 tack of ilaygadaKiaa of •adrla. fiwalao aa SXC9 far
a/« §7 la taa ro«aa«laa uaa wladav baevaaa 4,4'-oos
aad aadoamlfaa valfatat ooaflxs taam taa ataadaaca
•f-a/s «7 at taa rotaatloa Uaa of aadrla aldabyda
la <10% that of a/s «7 prndaaad by aadrla.
9.2.5.3.5 Lack of docradatlaa of 13C.,-4,4'-OOT. txaalao SICTa
•12
fa* a/s 291 aad a/s 247 la taa rataatloa tlaa window
taat lacladaa 4,4'-ooo, 4.4'-OCE, aad 4,4'-oOT: a/s
2M w««ld ba prodacad by 3C13-4,4'-oo«, aad a/s 247
by aC15-4,4'-OOO. Canfira tttat taa total abuadaaca
of ba«a laaa U <5% of a/s 247 producad by 13CU~4,4'-QG>?.
C-15
-------
9.2.« ftaalieaca Aa*lr«aa «< C*ta — U all parroauaaa encarla &r«
•aalyaa on* 1- or 2-rU, 4liqoo« e£ «*c& o£ tha ochar four
9.2.7 Xaapaaaa Factor C&leol*eloa
9.2.7.1 Calcalaca fftva raapaaaa faceara (W») far «aeh paaclcida
•aalyva, Ka califeraeloa eaaaaaar, *ad sarroqaca coapouad
(Saa Saca. 12.3.2), saaaaaciur«aa-d10 «ad
• iataaxaca* iaa «toonaaaca a< qoaattsaeloa
iaa far a paacieioa. * yea
coa^aaar ar a lonra^aca cc
ta*«»r»«a* toa atowaaaaa at a/« 240,
aa «aa iacaraal scaaaara «g a/s il«. «ha
faaavitaeiaa iaa wfeaa paaaaacAraaa*410
la aaaa aa tfca lacanal ««aa4ar«,
or
aaUbraciam aeaaaaar or rarra^aea eaaaauad.
la a ooitlaaa aaatoar« mLta oaa4 ca
aa a^olvalaaa. Ha«at THa dj-PGI eallaraeiaa eaaaanar
ba raaal^M teas alaaa-UC. £2 aa«, alyha-IK will
i*«ta ta cfta iaa aAoadaaaa aaaaoraa far C12-K3. 79
" far dtu eaa«rtba«ioa, «oftcra«« «.r% g< e^a iaa
o< a/x 219 aaaaora* for 4ipha-WK fraa Ua iaa
aaa aaaaora* far a/i 222 far
9.2.« Raaamaa Faetar Xapradwaiailicy — Far aaafc paaxlclaa caalrea. 7C3
caaaaaar «ad surraaaaa eaaaaaad. ealaalaca cha aaaa W
at taa fivo OOJ. MM* tha RJD aMaada 20%,
rlaca OU ca obtain
taa aa«lra eaaaaatra«loa raa^a. ar caJca ««ciaa ca
9.2.9
9.1.9.1 Yd aa«aaiaa«iaaa - Atoala«a racaavlaa elaaa ot »C1 eaa^aaars
•77 *a* «1Q4 shoaltf na« vary by aara CAaa «10 • frea oaa
aaalyala ca caa a«c«. (ftacamiaa tlaa raarodnelbilisr i*
aa« «a arltical for eaaaaaara »t tad »209 aa for «?7 and
• 104, «4Heft 4ra oaad ta oacacalaa wtiaa ton sa«a «r« eftanoad.)
9.2.9.2 faa«ieioa daxatainattona — Aaaaloto ra«aa«lon claaa a<
ordaaa, cadoaulfaa I. ana andaaulTaa ZZ shaald ne«
by aara c&aa ^10 • fzoa oaa «aalyala ea CJta nan.
C-16
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9.2.10 to cord a spaoanB of MCS CAL
9.3.1 Witfc tha following proeaduraa. *«ri£y initial calibration •« tha
hoftnnlaa- aad aad of each 12-a pariod during wfeich aaalyaaa «ra to
ba paxfocBad.
9.3.3 Calibrate tat ewa tho Hi with acaadarda and prooadaraa praoeribod
by tfca
9.3.3 JUMirM * 1-«L or 2-vL aUqv« o< ttM OTT»» M
Hi eaUteaUaa aad parforaanra (Taftia 4).
9*3.4 Ia3««« a i-«& or 2-«L allqvM «rf tfta Hadioa Oft and aaalyn
«aa« cvadl&loaa oa«d 4wia* Xaitial CaiUratioa.
9.3.3 Oaovaatraca accvpeaala parfosaatwa far erttarta daaartbad la S«ce.
9.2.4.
9.3.4 OacaaOM ftha* aalthar tte araa Mamrad for a/a 240 (or ctoyaaa*-^!2
ttoaa Car a/» lit far phanaatrtrana-4^Q haa dacroaaad by aora cbaa 30%
aaaavad U tha aaa* racaavarrvtooa aaalyala o< a
aalaaiom ar by aara taaa 50% froa tha aaaa araa
ialtial ealU»ra«Xaa.
9.3.7 Raapaaaa factor teyrodaelbilley. — for aa aeeap«atoLa Cantlatiin^ Cali-
bratioa dock* tha aaaavrad IV for aactt aaaZy^a/aurro^afta eoapouad
aaa« ba wtchla *JO% •< tha aaaa ralua ealcola«ad (S«ee. 9.2.7)
laittlai CaUttracioa. IS aoc, raaadAal ae&toa ana« b« eakaa;
aay ba aa«aaaary>
9.3.1 S2X taaiyma Ma«aatOoa ttaa HaarodualhllXcy — 0«aaaa«raca aad
M*ap«ahla (Sa«a. 9.2.9) raaro4a«l«Uley at abaola«a r«««attae
of aypropriaca paaUcida «aaiy«aa aad Kl racaa«loa tiao eoa^anaes.
9.3.9 faaadlal aotioaa aoa« ba takaa U eritarla ara aa« aa«; poaaihla
i arai
9.3.9.1 OMOk aad adjuat « aad/or « oaaracia« ceadlciona
9.3.9.2 daaa or roplaca iajactar Uaar.
9.3.9.3 Flaah ooliaai «l«h aolvvatt aa«ordla« to
9.3.9.4 Braak off a ataon portXom (awroAaataly 0.33 a) af tho
ii e&acJi oalaaai parfooaaoa by aaaiyoia of parfo
9.3.9.5 MofUoa QC eolaavt parfoaaaca of all Initial calibration
than raojolrad.
9.3.9.4 A4]ua« MS far Creator or laaaar raaolation.
9.3.9.7 Calibrata rtf aaaa Mala.
C-17
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9.3.9.9 Yraaara and aoalyxa naw concentration calibration/
aarracaaaca c&acfc aalatiaa.
9.3.9.9 Vrapara now concentration calibration corrals).
10.1 uaoMfOxr uftonrr suuoe out — Mrfam all s«aaa ia th« analytical
(Saaclaa 11) ualaa; all raa«aa«a, •caadarda, rarraqaca ccaaooada,
w«« aaaaraeaa* flAaawara, aad aalvaaaa taa«. would b« oaad Car »
aaalyais) ba* oait «a allqaae at saaaOa (waca» o* aail/«adlaaa«).
aaalaa, saAavitBCa 1 L aC raaaaac «««ac. Z
P»-pru»ldad raaaaa« blaaft aaild aa«arl*l far aa
10.1.1 ia CU ana* caat&ia tii« •«•• taeuaft of sorraaaca eaapooada «nd
la«ac9Al ctaadarda eiuc i« addad ca aacH •••ala. SUJ aaoua-e
vtll *»rr wl&A *aaala «rpa aad wtea caa eypa of da«a
or SIM).
10.1.2 Aaalysa aa Uta bafara aay savalaa ««• «rtraec*d aad anal7«ad.
10.1.3 Sataca * aav bates of aai*aa«a a* r«««aa«a U oaad Car ««aaL«
av«xaa«laa a* tor aaiiaam dtrraMtnyrayhtft araaaduraa* aaal/«a
aa UB. Sa addltxaa, aaalym * Ufeantarr aalvaa« bUak (U») ,
la ttta MBM aa aa CU avaay* eftac aa «arraaa«a eaaaevada or
adwda ara aadadi thia i1aaaa«trn»a taat raa^antts
caacaia aa taaaa«lt*«ioa iaaa Car taaaa
10.1.4 Aaalr«a aa Uta aloa^ wtcA «ae* batch of ^20
10.1.3 Aa aocaauMIa U9 contitna aa aa«had aaalrea a« a «aa«aa«ra«laa
araaca* eaaa aaa half of ita MOC aad ronritni M addl«taaal oomaauads
wtttt «Aa«taa cJura«Barl««laa aad aaaa jpacigal Saaeoraa sAae would
IscacSara «is& Uaaxl^lcacxaa aad aaaavr«aaa« of a aa«ted *aaiyt«
a« l«a m* £S taa Utt BB«« waa «a«raecad alana; wiea a baeeft of
La roair aal nairad Kba «a«Xra bacen of •••al««
tad aad raaa*lr****
10.1.4 earvaa«lf« avtlaa. far «Maaa9«aala Utt — da«k aa
aad fl«aaMara ea laaaca aad altaiaa«a taa aougea of
bafara aay laaaUa ara a«txa««ad aad aa«lr«ad.
10.2 GttXBMSZai — laaladad aaant ^nf*^1 aad namlnalm oallbraciaa proc«dur««
eallarattiam aftacfea ara aaaaByiiaaad with raaule«
«aa aalsciam, tfta aadlia* Laval e*llbr««iom aaiutlaa ear
laca tf«a of data aeajouxtiaa. aittar fuil-ranaa ar
10.2.1 X£ MB* orltarla ara net aa« ear a eaaclaolaa; C*ilir»eioa Chock
a£ta* * 12-ta pariod
-------
10.2.2 Vhaa aeaa* eritarla la Sa«t. 9.2 ara not, M«, mult* for affactad
aaalyeaa ana* b« Labalad aa raapaet to alart tha data aaar of taa
obaarrad problaa. Zaelodad aaaaa; theaa eritarla am raapeaaa
factor eaaex for «ach aaalyta ar fa ealltoratloa coaaaaar, daara-
da«10a of DOT and aadxla, and vataatloa tiaa rapradueiblller
SZM data iiiyil iirina.
10.3 UUIULE, LiVIUHnUffZO* OT UWMSO0 CJtfMZLZTT fO* iam MOLTSB
(Xaavfflelaa* laftraatlaa la ewr«a«lr av*xla»la far liannamn in far
•all/
10.2.1 Oa«il apavoarlaca Qoailer Caatral OMek Saaplaa ar« aralla01a.
•aatt LiDoracary stwold prcpara aaa ar aara aalaclaaa eaacalala^
aa«a aatted aaalyca at a coa«aatratiea eectaaBundtay «o that aatlel-
pa«ad la saaalaa. Oatil a«eva«y aad praclalaa llalta iuva b««a
aatabU«aad far »C1 laaaar froaaa la asfraprlaca laaplaa, a aalotlea
aa Axoclar alxaora aay »• oaadf eaaaara total aaaatsrad
ratlaa oa taa tatal Are«ler eoacaatratlaa. Xapore
ttratlaa aad aaaaorad eaacaavraelaaa «£ K3 tioaar
total aaacorad td «aa«aa«ratlaa.
10.2.2 Add aa cperaavlata valaaa a< a *ala«laa «t aattiad aaalytaa
«• •••* •< Sao* l-C, all«^a«a af raa«aa« «atar. firtravt aad
aaalr«a acoardiaa; ta avacadaraa ia Sa««. 11.
10.2.2 for aaaft aaalrta, ealcalata aaaaorad eeaeaatratlaaa, ralatlra
•caadard da^latlaa of taa four aaaauraanta, aad aatAed hiaa
12.4).
10.4 UUOIUSOXT fntPBMAItCX CUQC SOL3VIOV — Za "M - aathad* tha naitlna it
aeaaaatratloa aallaraclaa aalmloa alaa aar^va tha porpaaa a< a Uboratary
aatfaauaea attack aalatloa.
10.5
rf bach iimuaata eoBpavada la
aeeaptaaaa Ualta hara baaa aataaUahad far
tte fallowla* aaidallaaa ara providadt
CM • -JW «• *10%» aaaaorad biaa with
• -40* ta «2S«.
10.4 QOfcZTT OWIMi. vjgfl saionx — Ham ra« amllaalai aacletaaca aa«d far
f ^20 laaajlia. It fullTaaav data ara
aaaly«aa «aa ba avcaralaad wlta aaa
»M amraa«laa aad o*« OC/1VJ aaalyaaa
aad paatloldaa.
10.7 LMOU9OKT SVO3D OOftSASS UMfLS — S«la«c aaa iaaplt from aacb batch a<
i'fl iaaplia at •lallar trpa aad fartlTr (*•!*•> tM allo^ou a< taat saael«
»lta a Mloclan eeatalalaf «pproprlata eaac«atratloaa e< paatlalda aaalytaa
aad at Uaat aaa Aroclar alxtva. AT tar addltlaa at ««rroaata eoapeuada,
ajreraot aad analrta (S««t. 11) taaM tw« farU^lad all^at* aloaa; with
aa addttlanal uafartlflad saaaOa alJ^aot. HaUtlTa dlffaranea (W) aC
duplleata ramle« tor nrraaata cnapaniid eMMaatratlana «tto«ld ba <4Q\.
C-19
-------
(» • [C, - C2 / 0.3 (C, * Cj)l 100 ) Calcalata biaa aat la a 230-«b trlaaaarar Sliatt. Add * *aeaad
«»Iavi of aatitfloaa e&Larlda ea tfta ••••X« bo«tla «ad
rapaa« e&a ••craotioa acaaaduM « taeaad
efta anxmeca la taa ttlaaaaya* £laak. >«rfatm 4
la t&a *aai
(X-O) eaaaaacxatav by
11.1.1.4 Vaav taa nartlnad axtraam la«a 4 aal
10 OB o
«ita 4 20 ta 30 ad oartxaa of
ealavlaa. 4ad 4dd tfca rlaaa ta taa drrlaf caluan.
11.1.1.S Add oaa •» CM eiaaa balO^av olUaa ta taa
Claak 4»d 4ttaA 4 tftr«a»aall Sard** eaLuam.
taa Sayoax ealiua* by 4ddlaa; 4aawt 1 at of aacftylmo
ealotlda ta efta eoa. rlaaa taa K-O 4aoaratau on 4 hat
M«a» ba«a (aO-«S*C) aa ttta* tfta ceneaa«r«tar tua« I*
partially laavraad la tha hat ««ta*» 4ad tha «ntlra
IOIMV rovdad awrfaaa of taa Claak U batftad wlt& not
T«aar. Adjoat tfta vanOeal poaltlon of tAa 4aaax4tna
C-20
-------
u-o
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v vav» TB 01
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ae;
C'fll
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n «•
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rr»»oq
ao«2
»»n*
Ba BBBTJ
t»
IB-OS • •
/TTt» ae;
r;
i*fu
«&rr»«
ea
BS*T«tfB«Mv —
»BBBTB»8/TrB« fl'U
»*a»np««* "JB-OOOI • Ba
qa aa B7»aoq rrd»w
T»«T*T»B B^a BrfvzBaBo ft
aT BBV >r»rr3 Bqa
i -5
sa
01
ea
BeT%*«a
Ba
*I»BC rr n
Btja
90 7B OS PP« '
a JCTT
fl'l'U
ea 37
01 »B»»I a* ae; TBB» BB*
a«a»*» Bqa Boa? namndo* o-l
ft> BVHTBA »B«2«dd» Btja BBBJI
BB«BBpBB»
B»BJ aBdoad B^a av *«TB ot-6l
ea
-------
11.3 CC/M
11.3.1 taawre the sample extract or blank froa storage and allow it to
eae laboratory temperature 12 oeceaaary. with a stream of
filtered aitroeea, reduce the extract /blank volume to the
appropriate volume, depeadiaa; «» aaticipeted aaalyta concentrations.
aa appropriate volume at the •yprapviaea ia««rmal «taad»nl stock
11.3.1.1 Xatunul scudacd eaMwitrmtioa far f«ll-ffaaa«
11.3.1.2 Zatanal »taad«rd eeao«a«ra«iaa Car SIM data
• Q.79 a^/at «<
11.3.2 Iaj««« 4 1<-q& «r 2-«C. «Uaj«0« a< taa aiaak/saaala extract lata the SC
mder caadltlaaa tued ta pradoce acevvtaale reaulta 4uria«
11.3.3 teejoire aa«a •aeecral data vita eltaer («U«raae« data teajolsitlaa
•aaditlaaa a* SIM oeadlUene, «• aperaenate. ?«e the •••• data
•eojiaaltioa tlae aad Mi operatXaf caeeUtioiw pre*ie«aly ued to
deteralae reepaaae It
11.3.4 TirMlne data tor satsvated laaa ia «a«a ifectra
if satorat^ea oeevred. dXlate aad reaaalyse the extract after the
«joaa«lrr a< the tataraal itaadarde U *dju«ted aosraerlately.
11.3.3 Foe eacft laterual rtaadar*. determlae that the area aeaaqced ta the
evtraet hae aom ieereaeed by >30% froa the area aeaaured
the aevt reeeat arevtooa aaalyelj a* a cali&ratlaa •oitttlaa
er *f >SO% Sroa the aeaa area aeamred dorlAf Initial «aiibratian.
If either ezltariaa L» aot aat, reewdlal actlaa eoat be takea ta
iaprore seaaitiTtty, aad the saaaie extract aaat be reaoaiyted.
nta
11.4.1 Oaiae; the iaae ia»*« la Tafelea ?a*7« far Vda ar Taste 9 Sat
pre
-------
11.4.2.2 Obtaia iataaratad abwdaaea areaa for qjuaaeltatlon aad
fttiaa ieaa.
11.4.3 SZM Data — Obtain appropriate selected ioa eorraat profile* (SIC7»)
far ZS qoaatltaeiaa «ad eaafiraatlaa ioaa, for eaea Ion aaaiterod
«o data** peetieidee aad ete surroaata compound* (Table 9), and for
taa *jaaatlta«loa aad caorlasatloa iaaa far e«ca KB i*oaar ?roup.
11.4.4 Kl Aaalytoa
11.4.4.1 for «il KB aaadldataa. eoafixa tha proaaaca of aa («-70)*
iaa olaatar by ewaortnlae; XC9* or «pactra for *« IM*« on* of
taa aaa« iataaaa laaa la taa cyeraarlaea iaa eiu«ar.
11.4.4.2 for Clt^Cl? iseaar oroapo, ewoaina XC3>* or spectra for
aaa)la, i«4% af tha aroa aaaavrad for a/s 322 should
ba Bttbtraatad froa tha area aaaaorod for a/s 324, and 10«% of
taa a/s 322 araa shamld ba sobtraerted froa tha aroa aaaaurod
far a/s 32« (Tabla 13).
IO« or spacers for
(*»1SJ* iaaa that <»ejalit iadleata a eoalatXae; fd
additioaal a&larlaa. Tax* eaalatXan cause*
laaaaaa of **^ aatoral abBadaaoa of ^ ^C.
CSt&» iatarfaroaaa will ba ssMll aad eaa ba aafl*«tad except
.) Ta oarreaa far thX* iacarforaaaa, obtaXa aad
tha araa far taa appauaalata lorn (Table 14)
(!*»D* iaa data ta oalcoOata tha ratio of tha aaaaured
peaii aroaa of tha qoaatltatlaa iaa aad eanflaMtiaa iaa(s), and
ooBparo ta tha acceptable ratio (Tabla 9 for paatXeldaa and Table 12
far fda). IS aceeptabl* ratioa aro oat obtainad. a eaalatXne; or
partially coaltssiaa; ooapoqad aay ba iatarf erinc. Zxaaiaatioa of data
from sawaral scan* aay prorida infonaatioa that will allow application
of aAdltioaal baekeroqad correction* ta iaarowa tha ion ratio.
C-23
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11.5* zJJUMxrxc&rxoM exxszita
11.3.1 Xacanal Stiadarda
11.3.1.1 CJsrr««B«-<412 — ftna •buadaaca at a/s 241 r«La«iT« to a/x
240 aaa« ba ,>13% «ad <2S%, aad c&aaa ton* aua« aaxlalxa
•lault >aaan aXy. tha axaa aaaavrad Sor a/x 240 BO*C ba
vitala 30% atf eaa •»•• aaaawad dorlav ta« aoa« racaae
ealiaracioa.
11.5.1.2 »«a*a«ar«a«~41 0 — to* «buad*a«« otf a/i 10» ralACi-r* to a/s
b« £10% aa* O2%, «ad «&••• lea* «u« aayiai »•
Th« «ra« a««««v«d for a/i it« aore b«
30%. at tH« «*•« aa*«w«4 dovta^ ea« aeve rveaae
11.3.1.3
11.S.2 IMU«IUa4« teca Jar »w«laida Aaalyu* *«* Sum****
11.5.2.1 M«aa«l«a ciaa a* ta« ••••!• ««Bpaa«a« atwc a« wtsaia « *
atf tJM claa ota«xv«4 to* «aa« •«•• auapaiutil «ti
waa «aalr*a«. Caieola«a ctta valua o<
. « • (le)1/^, «Har« IS • oba«rv«4 rvcaaclaa
(la Meoaaa) a
11.5.2.2 All iaac vteft raiaciw atooidaaea >10% iA «ba aaaa
« la caa aaaa sp«««raa a< caa eaadldtea s«a«i«
* wlamlac laa wlea ralavlf* «aqadaaea >2* in
na aaa« ba ?r«a«a« la cha «aadlda«a
11.5.2.3 •»• laa «aa« ««a t&a aaa« «boadaa« (baaa paak) la «ft
a* «aa baaa ?««k la «aa eaadlaa«a
11.5.2.4 ra* Ul laaa with ralatlra ttMadaaaa >20% la tfta scaadard
•a««*nB, efta raUclva ifttiailiaaa la caa eaadlda«« •?•««•
aaaa a*a *a*y by aara saaa «13% la pareaaeaa* \«X«a (!•••,
U 10% la ««aada*«. max ba'%35% tad, <«S%).
11.5.X.5 Zaaa wlta tatatlra ifcaadaaa-a >10% la taa aaadlda«a
Car by «aa «aalr*«« *«• '*•«* 7recaaau»9
«a«4 «• abaala oaadldaua •faotra, boca pcoeaaaa^
ba avaloacaa.
11.5.3 S3X Oaca »aa*loida Aaalyaaa aad. l«m^a«a C
11.5.3.1 XbaalBta rvtaaelaa tla* a< aac* mrraaata eaapeuad &ad
paaxlolda eaadXdaca aaa« ba wttiiia 10 • at tfta«
tfca La«« pravlaua «ce«eubla
11.5.3.2 All laaa aaaltara* far aacft eiay d (Tabla 9) auac ba
praaaa* «ad aoa* aa«laX
-------
U.S. 3. 3 tn « apacem tvaraqad acroaa • « paifc tad with baek^rooad
carracbloa, 12 aaeaaaacy, tha aaae 4&uaduc ion auae
wttft «abla * data.
11.5.3.4 Oaaarrad ralaeiva •boadaacaa of eaa ae&lcarad ioaa suac
aaac taa fallawlaa; critariat
VLdrta — a/* 2«3 • >20% cad a/s 2«3 • >13%
|9C (3* «ad m/a
X «ad IX — «/s 339 • >3M aad a/x 341 • >20%
mLe»M — •/* 274 • 40-99%
— •/« 2«3 • ^30%
•Iteiird* — •/« 34S • >10%
IM-COM — •/« 317 • _>3»%
— •/! 271 • >30? «atf a/s 274 •
•paalAa — a/s 3S3 • >4fl%
Lor — a/s 221 • 3-30%
rrarrtitnr — a/s 407 • 43-93%
11.5.4 roll-taa^* «ad sm Oa«a far
wltaAa £10 • a* taae aaaaorad 4urla« taa L*a« jrrrioua
11.5.4.2 fl«aa«lta«laa «ad eaam la Tmala 121 •« laaa« oaa laa la eaa (»-7Q)
ba
12. CatOTULTIUM
12.1 PTW apf>epclata XO« a< qoaatlutlaa laaa, «baala «ad raaard Ua apace
saaaaa' otf caa ajvaaaaaffaajaXa paak tpaai aad taa traa 9t sh^ aadxa
raphla paak.
12.2 For Vda. s«a taa araaa tor all Uaaan Idaaeiflad 4t aach l«ral of
ealarlaaeiaa (a.f., *oa all ^oaavltatiaa laa traaa Car Cl4*Vda).
12.3 CalcoUtta taa caaeaatra«laa of ••« •tsr*a^a«a eupumid, paaclelda
eaadidata. «ad Kl laaaa* iroap oalaf tha
C-25
-------
»ara Cg • eaacaatraeiaa (aieroor*** par fcilovriai or aicroaraaa
aar Utar) of lurreaaga eoBeaoad. iadirldual pavcleida
or * KB ijoaar oroap*
A, • taa ATM of taa ojoaaettatlaa iaa ter aaea paaticlda
Aaalyta/iua iuaata ccaioauad or taa ma of «juaa«ltaeiaa
1*» iraa* for Ul KS iaoBMra AC a particular Laval
of
• tha ATM of th« laearaal •«aadard qoaaelta«loa tan,
a/s 240 far earjiaua 1^3 or •/* 1«« ear aaaaaa«hraaa-4iQ,
(aierofTMM) of latanal •cudard Addad ca
taa arcracc bafara QC/Ni
XT • ealeolacatf raapaaaa faeear far taa «urTO«aea eoapound,
taa aartlalda reaadard. or taa KB eaUara«laa compound
far taa liraiar arovy (!•*•! of eaiartaactoa), Aad
(lOlaaraaa) of »tm^» aMraeead. ZS A Uajoid
«M onraccad. 9 tmraaaa T, t&a wli»a
-------
12.5 ftapan oalcala«*a valo** ta «•• significant fiov**
12.4 MM* atBpl** of teoowa coapoaitioa or far&ifiod *«Bplo* ar*
ealc&Ue* ta* pareaat aacte* bia* aaiaa tha oqaatioat
• - 100 (C, - C,)/
«r ataraaraB* par Utar),
ta ta*
•otat a* ala* ralu* roealaa a po*itiT* or oaaativ*
13. AffTOMXT8P SSPffl/IvIATSOM AMD HLVSU^PfRff
for attaaA«*4 tteaclfieaciaa aad
fd« (I) uA p««%iald««. Ottyro«M<«d «C/W
Mr MOB pa««ici4« ••* MOB TC* !«••* 9*0*9 1* eai«aiae«d «tt
OUb^ia«tau«l for fwavr la^anacioa.
14.
7a ote&ia tia^l* lAAoratDty 4eearaey «a4 pr«el«laa dtta for aached 40*1-/tM,
rapilemea 1-t «Jj^ooca o< r«M*a« vaear «ad ri*«r «•«•«
«awa«J of *BAly«M war* *HU»«I*A «a4 4aalr«*4. tauaat*a aroe*dur«« «*
«• itfaaclfy «a4 a*aa«r* a*tha< «M!T«MI la 2««L Allo^Ma of 1-«L
••**•*• • raffi«i*B« o^aacier of iativlrfaai KM caaf*a*cs Ma* oac
Ar««l*r aixtw** war* oa*4 «• fartl^r «•«** ••plo*. T&i« U ao« o**iraal*,
ta«*a«* iatflTltaal VCB* ia Aro«Lors vary la oMcaatxscloa. A* Aroolor eaaewt-
will Call talow ta* «*«**cl*a Ualt «*4 will a*« ta M**ytfi*a
Za *adl«iaa, iA*offiot*a« daca ar* •«mll*01« «J**t Aroclar ggapaattloa ta «*••*•
**eara«r «< iaoa*» *r*ap aa**a**a*ac* or t* •*•*•• MDU far VC1* «d*a Axoclors
•r* «••« ta fortify •«
14. 1 ••*!»• t^wl a****a« v««ar fictratfca — ri-w «U^a*«* of r**o*a« va
vita «•*• latflTtdaal »**«Mi«* •« 4 o*a**a«ca«loa of 10 «*/L aad
1231. 1242, 12*4, aa* 12M 4« n*a«aamUua* of S «•/&, 90 «*/L,
$• «*/L 4*4 2S
4* of *2^ far 411 21 »*«ci«ia** (T4»i« IS), far iaainteal p**«xeld**,
f*r *ateia 4loaBy«a. «• «ra* vala** 4r* laaum far eaaeaatratlon* of
va* 110 a*/b (UD 2.9%), «aiea iaaiaa«*4 4 **tta4 bla* of *13%. for
la4iTlteal Heaar «roap*, MO* of a*aa *aa*w*a eaacaatxaeloa* raaovd
fraa 3.*% ta 16%.
14.2 Low trral x****at v*tar fictzaet — N****a« vatar «** far«l£i*a with «*ca
po*tlelda *t « eone*atr«eiaa of 3 «•/!• «a4 « tatal PC3 eoacontraclon of
27 4«/L (&ra*lacf 1221, 1 ao/Li 1242, 10 «*/lj 1254, 10 uo/T,; aa4 12«0,
C-27
-------
Waaa aavaa roalicata cxtracta *wra aaalyvad^ aatbad biaa for
iadividoal oaatieidaa raaoad from -17% ta *20% vita a aaaa aathod hiaa of
-2% (Taala 13). Aa MCZ, vaa caleolatad for aaca paatieida uaiao; tao oquatioa
r«latiao: tao standard deviation of tho sawa roolicaea aaaauraaoat aad
seodeat's JB mloa tor a oao-tailad taac ae tao 99% eaafidaaea lovol vitft a-t
doonoa of~froodoB d). Wita tfti* calcalatiea. not, la dafiaod aa
tod la wraaliaciaally low Wta raao^av froa 0.2 to
tor paattLaiaa aaaly«oa (Taala 13). A KB «, ia aa ladiridoal
raoeariatic aad oaaaoc aa dotaxviaod victi saBalaa for%i£lod witb Ajredor
roa. CatiawftM of HOta far iadirldaal eaapaamea of KB iaoawr oroopa
tacal o^uacity aaaatvod for ««ch Uoawr
iadiTideal KBa alao woro «ar«ali*xicallr low (0.01-4.1 io/t,> bocaoao of
cao oacalloatt prooiaiaa of aaaaoroaaaea. A aara ra«lia«ia ««a«aaaa« of
da«octiaa Uaita tor paacioidoa aad KBa eaa bo favad ia Soct. 1.2.
14.3 Xirar vaear txeraesa — n** allo^aaca of riv«r *a«or foreifiod vita
•aaa paa«icida a* a eeaeaacraeioa of S uo/L aad total KB eoaeaaesatioa
of 70 tt«/t. (Aroalora 1221, 2 «o/Li 12«, 30 ao/bi 1254, 30 a«/Li aad
1244* 4 »o/t) ««ra «Ara««ad aad aaalr*od. Mo«Ba4 biaa for iadivtdual
aaaxieidaa raafad firoa -30% ta «4% wteh a aaaa of -4% (Taalo 13). no
oaeallaat proeiaioa of aoaaorod p««tiaido KB iaaaar croup eeaeantratioaa
«aa iadleatod by MOa raa^la^ toaa 1.4% ta 7.3%. •»• aaaa aaaaurod total
eeaeaaaratioa of 31 a«/L (TOO 2.3%) indicated a aattad biaa of -27%.
13.
1* Aaaar. J. A., 0. t. r»an«, 0). 0. NcKao, 4. A. Qoava, aad *. &. tadda,
2. lalUoaaitar, S. aad N. Sail, froaoalaa Z. Aaal. O«««, 302, 20, 19*0.
3. *Careiaooaaa — T*or*ia^ wiea Ca*«iaa«aaa* • Ooaartawa* of Boalfia S«rrtca,
•Careiaooaaa — Mrxiav wiea ca*«iaa«aaa-, ooaarsaaav ox aaa^sa
Caatar tor Oiaoaao CaacTOl. national Xaatxeaca for Occupational
aad faalta, *«alieatioa no. 77-204, Aa^ta*. 1977.
4. *Q4A Safo«r aad loalta Staadarda. G«n«ral Zadaatxy*. 29 CTK 1910,
Oaoojaatioaal Safaey aad laalca AAvlaiatracioa, 04A 2204, *••
*_^>^_ ««9A.
S. "Safo«r la HidaaH Oavlatay taa«ravrioa*, Haartttin Otoaieal So«iocy
sal Safoty, 3rd Kditioa, 1979.
4. «lUa, H. 0.» C. TaaJifnf, S. Hamad!a. N. MaaJaia. S. I. Safa, aad
U *. Safa, nuan Haoolotion KB Aaalyaiat Syavaaaia aad CtfomtaoraaHXe
of All 209 KB Caaaaaara*, ta^troa. tci. Tachaol. 14, 444, 1944.
7. fi«baarK, J. X*, ftayoo, T. t., Alfard-4tawaa, A. t>., aad v. t. todda.
of .
Grottaa*, Anal. Clam. 57, 2434, 1943.
C-28
-------
<»T» i nov p«* 3.0*1
OC
»*
R
*•;
•a*oic
3.01 TO
•CM a 09
n«p
EfO X • OC
f '•MV *t
-------
Taala 2. Yd Caa^aaaxa 3««d »« Calliraeioa
Chlorin*
Kl tjeaar Croup Mnaftir* Sobaelttstioa
Caaaaacvaeiaa Cali&rmciaa Staaaaxa
NeaoaaloraBlpaaarl t 2
Otealamatphaayl S 2,3
29 2.4.3
SO 2.2',4.«
feataehlorebiphaayi «7 2,2* ,3. 4,9*
134 2,2' ,4,4', 3. «•
tM 2,2t,3,4' ,3,«,
0«eMBl«roaLp)Meyl 200 2. 2' ,3. 2'. 4,5' ,4. •
209 2,2' ,3,3',4,4' ,3,3' ,«,«'
toeaatiaa Tiaa CAliiwtiaa
Tncaealanbipaaayl Tt 3, 3 ',4, 4*
MatactaoroatphaayL 104 2,2<.4,«.<>
2.J' ,3,3' ,4,3,5'
ta c&a *r*«aa «* l*U»«haAB«r aa4 Zall (2).
far be«h saoa-
C-30
-------
8 3 3 3 . „ -
sssrssSss
pppnppppp
-•*>«*«»»•*»*.»
O
I
•^ ^™ ^» ^» w^ ^^ w* ^»
I 1 I 1 1 I} I
Vrapa
fee
Oil.
Z
s
*
e
D
&
a
K-. ^ ^ _• _.
MUOOOMUiUi
ooooooooo
-------
ii
I 1
ii
3
3
a
!j
2 5
for
§1
sssssgsgsssssssss
oooopoooo
*-*-*-r«Mr«r«rtvi
ooooopoo
e o
j 333333533
o e
M
..•] «
M 6
999
5
JB e r M • q *
3ll|3« ^f
jifsro 1}
£i
»ii
hi
U II
CM
-------
Taala 3a. Hmynaluiun asd Appraxiaaca Coaeaatracioaa a< C*litea«iaa Solacieaa
tor SXX Oaca >c
-------
TU»la 9** C(•pnaiu.ua «ad Approxiaarca Coac*a«rae4.oaa of CaJjL£ra«loa 3olu«loaa
Caacaa'craclaa ( n «/ot )
Aaalyea/Ia«araal Std/
Swroaaca Csapooad
U<*rta
BK, M« 1— r
4,4 '-000
4.4'-C«
4,4'-OOt
Oialdria
tade.«l£«i t
TnrtnanUaa «
BMoaoUu .«U»ta
ta*rta
tadna Utettyte
btfria Icatana
lapcaealar
•apcaealar apoaldai
HaHtaaMa1ar
s.a-1^ aaa* *__
Qvyaaaa^f]
FhaaaaaJg aaa- *i Q
^^-^-MC
13C12^,4'HJOr
cat i
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.4
0.4
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.73
0.73
0.2
0.2
at 2
1
1
1
1
1
1
1
2
2
1
1
1
1
1
1
1
1
0.73
0.73
1
1
C-34
at 3
2
2
2
2
2
2
2
4
4
2
2
-
2
2
2
2
2
0.73
0.73
2
2
at 4
3
9
9
9
9
9
9
10
to
3
3
3
9
9
9
9
9
0.73
0.73
9
9
at 9
10
10
10
10
10
10
10
20
20
10
10
10
10
10
10
10
10
0.73
0.73
' 10
10
-------
T»bl« 4. Crltaria for ort»»
127
197
199
27S
3U
441
442
443
10*30%
-------
Tattia 7a. Xoaa for Salaetad Ion Maoita*la«; to 0««arBia«
Oa«a for Four *a«a of OS Xoaa
Vd Xaoaar Qroaa/
MaaaAlareaipaaayla
OieJOaraalahaarla
Tricfciarabiphaayla
•aatacalarablphaarla
laMchlarebtpaaayia
•aptaeblarablphaayU
OocaehiorottlahoarU
MaacftlaraUpaaayl*
OMactUaraatabaayl
«^,aa^12
"c.-~— -«:
13e.--4,4'-00T
N0** Wft«
1.0
222
294
290
324
390
392
424
440
494
240
100
294
344
Naaa or Maaa*
ta bo Noalearad
132i 104-190
220-224
294-240
2M-294
322-320
394-342
390-394
424-430
440-444
494-900
240-241
100-109
107,109
247) 249
na. of
Zoaa
4
3
7
7
7
7
7
7
7
3
2
2
2
2
Xoa 3«ca
•1 »a *3 *4
4
3
771*
7 7 1»
7 7
4« 7 7
44 7
7
7
3
2
2
29 27 24 33
at (M-7Q)* far d9<
at (H-7Q)* for
•/« 294 ta m
»*» a/s 210 «• iiiB
«« •/> 397 la
«« •/* 391 la Xaa
100 »nd 109 iaclAdad 00119 Laaa «»** to 4a«
107 «ad 109 laalaoM AMO^ lana uaod ta dac
•«aTva a
ud aaaaora aanacAlorobiphcnylj,
C-36
-------
•ION
'low »««»1 "HO*-13
•tl-CI
M»
ICC
CC»'9C»'9C»
9«C't«t'CM CC»'9C»'9C»'9C»
»«I'C«C'9«C
CC»'9C»'9C»
99C'9SC'9$C CC»'9C»
»CC'CCC 9«C'9«C'CCC
9«C'99C
9»C
9C»
"13
••AJ
•13
99C
-
ccc
ccc
-
ccc
«9C
ssc
-
-
ccc
-
-
99C
»sc
-
9«C'9«C'»«C'CCC
C9C'99C
_
C9C'99C
9CC'9CC'»CC
»«C'C«C'9»C
-
-
9«C'9«C'»«t'CM
_
-
C9C'99C
9CC'9CC'»CC
9CC>CC'CCC
9«C*99C
9SC'»SC
C«C'9«C'«9C
9fC'9CC'»SC
CCC'9CC
991 '991
9«C'CCC
C9C *9SC
9CC'»CC
C9C'9«C
9CC'»CC
»«C'9«C
9SC
»«C
99C
9CC
99C
9Ct
C«C
9«C
'la
6
MC
ICC
»«C'CCC'9CC
»cc'ccc
CCC'9CC
991 '991
»«C'C«C'9«C B99I'991'ttl'CCI
9SC'9SC qtSl'Cfl
SC«N
•t«N
•l-H
• 91
MC'9«C
9CC
»cc
9«t
••Of
991
191
etc
9CC
CCC
991
ha
'Cl
13
»*|J
-------
O
a «r
MM
O O «
B I Jt*
?
g S fi 8
»• IT
I *
ii
I I I i
MM
J / * i
O I I I
MM
I E
•«
/
M
S S !
a
A
*3
A
I
. if
» lr
a F^
* *s
l£ ^J 4rf fc^ 14 ^^ 4J ^* ^4 ^* ^^ ^^ fe* 9^ fr4 ^^ ft4 9^ 0J
«4B«JkCtJO««l»«M
A» LA LA 4^ bt CA ^4 t^A ^4 b4 t4 VA ^A bA ^j fc^ ^^ <
fj3«««i<*3*4k«AMUMU»j3B*>
Ha*»a^MS*^t»*»MOi§^
e- o o <* «•
O M O <• •
e
u uu w u if 8
» M O O » • M
u> A
i
?
cs
n
•f «I
*s ;!
«8
J
S
• it
-------
Table t. ftaeaaclaa
Oa«a for
•r <3r
•ad Calibration
Sronp
MaaanhlnrnotoaaaTla
Oiahlaroalphaarla
TrioalarabiphaayI*
Taeraaaloraolpaaayla
Paatacaloroblpaaay la
laBacftlorohiphaayla
•apcacfelaraaisaaayla
Oocaehlaroaiphaaylj
naaaahlegealahaaylj
Oaeacbloreatphaayl
kpproxiaaca
Mtt Saaga*
0.30-4.33
0. M-4. 39
0.44-4.44
0.59-4.42
0.44-4.92
0.7S-1.1
o.n-1.2
9.99-1.21
1.14-1.24
1.3
Cal. Caaf.
1
S
»
SO
47
194
144
200
*
209
Cal. Cong
Mtt*
0.30
0.43
0.54
0.54
0.40
0.42
0.44
1.03
-
1.3
a 30 • Z 0.31 am 13 tt-54 f
»Uiea capillk*? ealaM aa4 ea« tolla«la« SC eaadltiamat spllslaaa
*« 40«C; hold far 1 alAi haa« rapidly ea 140*C aa4 h«14 1 alar Laeraaaa *e
310*C.
C-39
-------
Tabla 9. t«n« tor Salacead laa Noai«aria« Oaea Aeqoiaieioa Co* »«acleld«
Xaftanal Seaadarda «ad 3 ------- --------- — '^-- ---- ' ^ -
ton
Aaalrca/taean
Surrovaca Cornea
Alpha-OK
o«ca-OK
«aa»OK
13C,~<*— -•":
»n.aaaea*aa^d10
Mea-OK
I«p«aealor
Xldrla
AL Std/
ad (MM
(2M)
(2M)
(200)
(294)
(100)
(200)
(370)
(302)
I«f«aaalar «paxlda(3*4)
liaaa rhlardaaa
todo.ul.-4fl :
JUaaa-ealordaaa
Tra»a-~acUa*
Dial drla
4,4'-0«
cao*ia
«a4amara.I2
4.4-«
MlatlfeArd.
(400)
(404)
(40«)
(440)
(370)
(310)
(37«)
(404)
(311)
(371)
taaoataUaa ml£ata(420)
4,4'-OQT
13Cia-4.4'-0«
Kadria kacaia*
C&r7Ma-4Y2
Na«Aoar«lor
(332)
(344)
(370)
(240)
(344)
Appro*.
0.43
0.47
a. 40
0.40
0.49
0.31
0.30
0.04
0.70
0.74
0.70
0.70
0.77
a. oo
a.oi
0.03
0.03
0.07
O.M
0.91
0.93
0.93
0.99
1.00
1.03
C-40
Qoaac.
ton
219
219
219
223
100
219
272
203
333
373
199
373
409
79
244
01
193
233
07
273
233
247
07
240
227
Zeaa (Apprexljuea
Xala^lT* Abundaaea)
111 (100), 103 (90), 219 (70)
101 (100), 103 (90), 219 (70)
101 (100), 103 (90), 219 (73)
1t7'(100), 109 (90) 223 (00), 227 (4
100 (100), 109 (13)
101 (100), 103 (90), 219 (70)
100 (100), 272 (00), 274 (40)
04 (100), 243 (40), 243 (23)
01 (100)., 333 (00), 333 (03)
373 (100), 373 (93)
199 (100), 339 (30), 341 (33)
373 (100), 379 (99)
409 (100), 407 (03)
79 (100), 243 (10), 100 (13)
244 (100), 24a (43)
01 (100), 243 (73)
199 (100), 339 (SO), 341 (33)
233 (100), 237 (43), 143 (03)
47 (100), 343 (30)
272 (100), 274 (00), 507 (30)
233 (100), 237 (03), 143 (43)
247 (100), 249 (43)
47 (100), 317 (30)
240 (100), 241 (20)
227 (100), 229 (13)
-------
Taala 10. Zaa Sata tar Salacead Zaa NeaAttariaa: a* Paacietda Aaaly«aa. tat«rn*i
(Ordarad by Ra«aa«4.aa tlaa)
Zaa
Zam Sa«
H
Meaiearad
•7
1«S
22?
221
US
237
240
241
247
249
271
274
317
34J
347
4.4'-000
tadaanlfan
4,4'-OOT
13C12-4,4'HSOT
tadria kacaaa
Mathoxyehlor
14 iaaa, •
13 laaa. 9 a
19 laaa • e
C-41
-------
1!
a«
N
fL
«oon*o»^m
r» »- o ••»»•»- r»
n r* «i ft
1 « f- r» f» •-« •
i »- r« o e a o
S"
•- O t- W i
• ^ f» O '
r» r> •- O • f»
*" H ^™ tO **"
•* • •» o »• r»
5 5 5 SS S
8
3
I
i
i
O«9r*M*-«
•» o»-ll«-r»
J «*
fro^n
• o •- n
f"
5
f
t
o «-*•-
•3 o f?
• t • • •••«•
01
6
35353733333555!
rt M
^ *
«RRR pa««««sss«s j
-------
Zatarnal Std.
tm
Coafiau
Zoa
Tabla 12* QoaaCitaeloa, Coafixaaelea , «ad Zatar£*raaca
lacarnal *e*adaxda, aad
Qoaat.
Zaa
OMCX Sou for
XMiO*
H-70 tat«rf«r«nc«
Caafifli. ea«c>c Ion*
Zoa it* 70 (t*39
* Sroap
Clj
Clj
Ci10
144
222
294
2*0
324
394
392
424
440
4*4
144
222
294
2*2
324
344
3*4
430
444
4*4
190
224
294
2*0
324
342
394
424
444
300
3.0
1.9
1.0
1.3
1.4
1.2
1.0
1.1
1.3
1.1
2.9*3.9
1.3-1.7
0.4-1.2
1.1-1.9
1.4-1.4
1.0-1.4
0.4-1.2
0.9-1.3
1.1-1.3
0.9-1.3
192^ 294 222
192 292 294
144 324 290
220 340 324
294 394 340
244 430 394
322 444 430
394 494 444
390 - 494
424
244
144
2*4
344
244
144
147
247
241
14*
14*
249
9.1
4.4
1.0
1.9
4.3-9.9
4.0-7.2
0.4-1.2
1.3-1.7
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C-43
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tea Maaaarad % of tteaa. Zoa ATM to
cudidata Qoaot. Confirm, to Ootaralao b*» Subtracted from
Zaomar Croup Zoa Zoa Zatar£a*aaca
TrlcftloroblpboflTlJ 234 234 234
'leaacaloroelpaearU 340 342 334
loptaealorobiphearU 394 394 390
TabLa 14. Conaaxloa for ZatarCaraaca of KB Coatalai
Zoa Noaaort
Caadldata Qoaa«. to Oocarmu
TrIealoroalpaaarlJ 234 233
tatraeaioroatpBOBf la 292 249
•AMAtfteLA0Bk^A^^^RPtA 34A 3S^
•^•^^IVBftOT^H^PHW ^^M^^c ^" v^^v • w *
OcUMmlawaCAplMaRr^ 434 433
Qoaat Confirm*
Zoa Araa ton Vraa
99%
104%
141*
233%
>a« Oaa Additional ca
id % of Maaa. Zoa
M to bo Subtract!
ta STOB Qoaat. Zoa
13.3%
13.3%
17. 4%
23.0%
24.3%
30.9%
40.0%
33%
144%
71%
123%
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